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Sample records for direct reaction sintering

  1. Direct Observations of Silver Nanoink Sintering and Eutectic Remelt Reaction with Copper

    SciTech Connect

    Elmer, J. W.; Specht, Eliot D

    2010-01-01

    Ag nanoink sintering kinetics and subsequent melting is studied using in-situ synchrotron based x-ray diffraction. Direct observations of Ag nanoink sintering on Cu demonstrate its potential for materials joining since the Ag nanoink sinters at low temperatures but melts at high temperatures. Results show low expansion coefficient of sintered Ag, non-linear expansion as Ag densifies and interdiffuses with Cu above 500 C, remelting consistent with bulk Ag, and eutectic reaction with Cu demonstrating its usefulness as a high temperature bonding medium

  2. Sintering of reaction bonded silicon nitride

    NASA Technical Reports Server (NTRS)

    Mangels, J. A.

    1983-01-01

    A process to produce sintered reaction-bonded Si3N4 (SRBSN) articles has been developed. This process consists of the addition of an appropriate sintering aid to reaction-bonded Si3N4 followed by sintering between 1780 and 2000 C, using an over pressure of nitrogen. The principal advantage of this process is the low sintering shrinkages of 5 to 10 percent. The properties and microstructure of two SRBSN systems sintered with MgO and Y2O3 additives are described and were found to be comparable to corresponding hot-pressed Si3N4 systems. Examples of applications of both systems are illustrated, demonstrating near net shape fabrication capability of the process.

  3. Reaction sintering of zinc ferrite during constant rates of heating

    SciTech Connect

    Rahaman, M.N. . Ceramic Engineering Dept.); De Jonghe, L.C. . Lawrence Berkeley Lab.)

    1993-07-01

    The reaction sintering of equimolar quantities of zinc oxide and ferric oxide was investigated under conditions of constant rates of heating and the data were compared with those for a calcined, single-phase zinc ferrite powder. For the heating rate of 1C/min, the densifications of the reaction-sintered sample and the calcined sample were approximately the same. However, as the heating rate increased, the density at any temperature increased slightly for the reaction-sintered sample but decreased slightly for the calcined powder. The factors responsible for this slight difference in sintering between the reaction-sintered sample and the calcined sample are discussed. For the constant heating rates used, the reaction was completed prior to any significant densification. Relative densities of >95% were obtained for both the reaction-sintered sample and the calcined sample under identical sintering conditions (1-10C/min to 1350C). Reaction sintering in a steep temperature gradient produced a nearly fully dense body prior to complete reaction; a composite microstructure consisting of fine zinc oxide grains in matrix of zinc ferrite was obtained.

  4. Computer Modeling of Direct Metal Laser Sintering

    NASA Technical Reports Server (NTRS)

    Cross, Matthew

    2014-01-01

    A computational approach to modeling direct metal laser sintering (DMLS) additive manufacturing process is presented. The primary application of the model is for determining the temperature history of parts fabricated using DMLS to evaluate residual stresses found in finished pieces and to assess manufacturing process strategies to reduce part slumping. The model utilizes MSC SINDA as a heat transfer solver with imbedded FORTRAN computer code to direct laser motion, apply laser heating as a boundary condition, and simulate the addition of metal powder layers during part fabrication. Model results are compared to available data collected during in situ DMLS part manufacture.

  5. Direct metal laser sintering: a digitised metal casting technology.

    PubMed

    Venkatesh, K Vijay; Nandini, V Vidyashree

    2013-12-01

    Dental technology is undergoing advancements at a fast pace and technology is being imported from various other fields. One such imported technology is direct metal laser sintering technology for casting metal crowns. This article will discuss the process of laser sintering for making metal crowns and fixed partial dentures with a understanding of their pros and cons.

  6. Sintered-reaction Bonded Silicon Nitride Densified by a Gas Pressure Sintering Process Effects of Rare Earth Oxide Sintering Additives

    SciTech Connect

    Lee, S. H.; Ko, J. W.; Park, Y. J.; Kim, H. D.; Lin, Hua-Tay; Becher, Paul F

    2012-01-01

    Reaction-bonded silicon nitrides containing rare-earth oxide sintering additives were densified by gas pressure sintering. The sintering behavior, microstructure and mechanical properties of the resultant specimens were analyzed. For that purpose, Lu2O3-SiO2 (US), La2O3-MgO (AM) and Y2O3-Al2O3 (YA) additive systems were selected. Among the tested compositions, densification of silicon nitride occurred at the lowest temperature when using the La2O3-MgO system. Since the Lu2O3-SiO2 system has the highest melting temperature, full densification could not be achieved after sintering at 1950oC. However, the system had a reasonably high bending strength of 527 MPa at 1200oC in air and a high fracture toughness of 9.2 MPa m1/2. The Y2O3-Al2O3 system had the highest room temperature bending strength of 1.2 GPa

  7. Sinterable Powders from Laser Driven Reactions

    DTIC Science & Technology

    1982-03-01

    4 flow rate on the resulting Si powder particle size (reaction cell pressure of 0.6 atm). 39 21. The effect of SiR 4 flow rate on the ratio of Si...should be expected, therefore, that the relative emissivity of the SiR 4 flame will fall somewhere between following a /K dependence and following...electron diffraction. The diffraction patterns were identical to those for Si powder made from SiH 4 . The powders from SiR 4 and C2H4 runs showed

  8. Sinterable Powders from Laser Driven Reactions

    DTIC Science & Technology

    1979-07-01

    18) line was based on information from the liter- ature (Tindal, et. al., 1942) rather than direct correlation with spectro- graphic data. Amonia ...number of lines to be measured; (2) laser intensity was sufficiently low to preclude virtually any heating of the silane or amonia . Two methods were used...manometer. Electronic grade (Airco) silane was used from the tank after many freeze-pump-thaw cycles; anhydrous (Airco) NH3 was treated similarly. The

  9. Reaction behavior of SO2 in the sintering process with flue gas recirculation.

    PubMed

    Yu, Zhi-Yuan; Fan, Xiao-Hui; Gan, Min; Chen, Xu-Ling; Chen, Qiang; Huang, Yun-Song

    2016-07-01

    The primary goal of this paper is to reveal the reaction behavior of SO2 in the sinter zone, combustion zone, drying-preheating zone, and over-wet zone during flue gas recirculation (FGR) technique. The results showed that SO2 retention in the sinter zone was associated with free-CaO in the form of CaSO3/CaSO4, and the SO2 adsorption reached a maximum under 900ºC. SO2 in the flue gas came almost from the combustion zone. One reaction behavior was the oxidation of sulfur in the sintering mix when the temperature was between 800 and 1000ºC; the other behavior was the decomposition of sulfite/sulfate when the temperature was over 1000ºC. However, the SO2 adsorption in the sintering bed mainly occurred in the drying-preheating zone, adsorbed by CaCO3, Ca(OH)2, and CaO. When the SO2 adsorption reaction in the drying-preheating zone reached equilibrium, the excess SO2 gas continued to migrate to the over-wet zone and was then absorbed by Ca(OH)2 and H2O. The emission rising point of SO2 moved forward in combustion zone, and the concentration of SO2 emissions significantly increased in the case of flue gas recirculation (FGR) technique. Aiming for the reuse of the sensible heat and a reduction in exhaust gas emission, the FGR technique is proposed in the iron ore sintering process. When using the FGR technique, SO2 emission in exhaust gas gets changed. In practice, the application of the FGR technique in a sinter plant should be cooperative with the flue gas desulfurization (FGD) technique. Thus, it is necessary to study the influence of the FGR technique on SO2 emissions because it will directly influence the demand and design of the FGD system.

  10. Pressureless Reaction Sintering of AlON using Aluminum Orthophosphate as a Transient Liquid Phase

    SciTech Connect

    Michael Bakas; Henry Chu

    2009-01-01

    Use of aluminum oxynitride (AlON) in transparent armor systems has been difficult due to the expense and limitations of the processing methods currently necessary to achieve transparency. Development of a pressureless processing method based on direct reaction sintering of alumina and aluminum nitride powders would reduce costs and provide a more flexible and practical manufacturing method. It may be possible to develop such a processing method using liquid phase sintering; as long as the liquid phase does not remain in the final sample. AlPO4 forms a liquid phase with Al2O3 and AlN at the temperatures required to sinter AlON, and slowly decomposes into P2O5 and alumina. Therefore, it was investigated as a possible transient liquid phase for reaction-sintered AlON. Small compacts of alumina and aluminum nitride with up to of 15wt% AlPO4 additive were pressed and sintered. It was found that AlPO4 formed the requisite transient liquid phase, and it was possible to adjust the process to produce AlON samples with good transmission and densities of 3.66-3.67 g/cc. XRD confirmed the samples formed were AlON, with no trace of any remaining phosphate phases or excess alumina or aluminum nitride. Based on the results, it was concluded that AlPO4 could be utilized as a transient liquid phase to improve the density and transmission of AlON produced by pressureless reaction sintering.

  11. Direct laser sintered WC-10Co/Cu nanocomposites

    NASA Astrophysics Data System (ADS)

    Gu, Dongdong; Shen, Yifu

    2008-04-01

    In the present work, the direct metal laser sintering (DMLS) process was used to prepare the WC-Co/Cu nanocomposites in bulk form. The WC reinforcing nanoparticles were added in the form of WC-10 wt.% Co composite powder. The microstructural features and mechanical properties of the laser-sintered sample were characterized by X-ray diffraction (XRD), atomic force microscope (AFM), scanning electron microscope (SEM), energy dispersive X-ray spectroscope (EDX), and nanoindentation tester. It showed that the original nanometric nature of the WC reinforcing particulates was well retained without appreciable grain growth after laser processing. A homogeneous distribution of the WC reinforcing nanoparticles with a coherent particulate/matrix interfacial bonding was obtained in the laser-sintered structure. The 94.3% dense nanocomposites have a dynamic nanohardness of 3.47 GPa and a reduced elastic modulus of 613.42 GPa.

  12. Reaction sintering of alumina{endash}aluminide alloys (3A)

    SciTech Connect

    Claussen, N.; Garcia, D.E.; Janssen, R.

    1996-11-01

    A novel pressureless reaction sintering process is presented for the fabrication of Al{sub 2}O{sub 3}{endash}aluminide alloys (3A). Compacts of intensively milled metal oxide{endash}aluminum mixtures are heat-treated in vacuum or inert atmosphere such that the exothermic reactions take place in a controlled manner essentially at temperatures below the melting point of Al. Dense, homogeneous microstructures were obtained with a variety of Al{sub 2}O{sub 3}-matrix systems with interpenetrating networks of aluminides of Ti, Fe, Nb, Mo, Zr, Ni, etc. By adding modifiers in the form of oxides or metals, volume and phase composition as well as properties can be tailored in a wide range. {copyright} {ital 1996 Materials Research Society.}

  13. Development of a reaction-sintered silicon carbide matrix composite

    NASA Astrophysics Data System (ADS)

    Sayano, A.; Sutoh, C.; Suyama, S.; Itoh, Y.; Nakagawa, S.

    SiC matrix composites reinforced with continuous SiC-based fibres using reaction sintering (RS) for matrix processing were produced and their mechanical and physical properties were studied. Mechanical behaviour of SiCf/SiC (RS) composites in tension and in flexure exhibits improved toughness and a non-catastrophic failure due to fibre crack bridging and pullout from the matrix, and the composites exhibit high thermal conductivity, high Young's modulus and reduced porosity. Moreover, SiCf/SiC (RS) composites showed improved thermal shock resistance in comparison to monolithic RS-SiC. SiC matrix processing by RS leads to reduced production times and lower costs when compared with other methods such as polymer impregnation and pyrolysis (PIP) or chemical vapour infiltration (CVI). Composite prototypes were also produced for feasibility demonstration, and it was verified that the method could be applied to produce large parts and complex shapes.

  14. Comparison of properties of sintered and sintered reaction-bonded silicon nitride fabricated by microwave and conventional heating

    SciTech Connect

    Tiegs, T.N.; Kiggans, J.O. Jr.; Lin, H.T.; Willkens, C.A.

    1994-10-01

    A comparison of microwave and conventional processing of silicon nitride-based ceramics was performed to identify any differences between the two, such as improved fabrication parameters or increased mechanical properties. Two areas of thermal processing were examined: (1) sintered silicon nitride (SSN) and (2) sintered reaction-bonded silicon nitride (SRBSN). The SSN powder compacts showed improved densification and enhanced grain growth. SRBSN materials were fabricated in the microwave with a one-step process using cost-effective raw materials. The SRBSN materials had properties appropriate for structural applications. Observed increases in fracture toughness for the microwave processed SRBSN materials were attributable to enhanced elongated grain growth.

  15. Comparison of properties of sintered and sintered reaction-bonded silicon nitride fabricated by microwave and conventional heating

    SciTech Connect

    Tiegs, T.N.; Kiggans, J.O. Jr.; Lin, H.T.

    1995-10-01

    A comparison of microwave and conventional processing of silicon nitride-based ceramics was performed to identify any differences between the two, such as improved fabrication parameters or increased mechanical properties. Two areas of thermal processing were examined: sintered silicon nitride (SSN) and sintered reaction-bonded silicon nitride (SRBSN). The SSN powder compacts showed improved densification and enhanced grain growth. SRBSN materials were fabricated in the microwave with a one-step process using cost-effective raw materials. The SRBSN materials had properties appropriate for structural applications. Observed increases in fracture toughness for the microwave processed SRBSN materials were attributable to enhanced elongated grain growth.

  16. Effect of attrition milling on the reaction sintering of silicon nitride

    NASA Technical Reports Server (NTRS)

    Herbell, T. P.; Glasgow, T. K.; Yeh, H. C.

    1978-01-01

    Silicon powder was ground in a steel attrition mill under nitrogen. Air exposed powder was compacted, prefired in helium, and reaction sintered in nitrogen-4 v/o hydrogen. For longer grinding times, oxygen content, surface area and compactability of the powder increased; and both alpha/beta ratio and degreee of nitridation during sintering increased. Iron content remained constant.

  17. Effect of attrition milling on the reaction sintering of silicon nitride

    NASA Technical Reports Server (NTRS)

    Herbell, T. P.; Glasgow, T. K.; Yeh, H. C.

    1978-01-01

    Silicon powder was ground in a steel attrition mill under nitrogen. Air-exposed powder was compacted, prefired in helium, and reaction-sintered in nitrogen-4 v/o hydrogen. For longer grinding times, oxygen content, surface area and compactability of the powder increased; and both alpha/beta ratio and degree of nitridation during sintering increased. Iron content remained constant.

  18. Strength of hot isostatically pressed and sintered reaction bonded silicon nitrides containing Y2O3

    NASA Technical Reports Server (NTRS)

    Sanders, William A.; Mieskowski, Diane M.

    1989-01-01

    The hot isostatic pressing of reaction bonded Si3N4 containing Y2O3 produced specimens with greater room temperature strengths than those by high pressure nitrogen sintering of the same material. Average room temperature bend strengths for hot isostatically pressed reaction bonded silicon nitride and high pressure nitrogen sintered reaction bonded silicon nitride were 767 and 670 MPa, respectively. Values of 472 and 495 MPa were observed at 1370 C. For specimens of similar but lower Y2O3 content produced from Si3N4 powder using the same high pressure nitrogen sintering conditions, the room temperature strength was 664 MPa and the 1370 C strength was 402 MPa. The greater strengths of the reaction bonded silicon nitride materials in comparison to the sintered silicon nitride powder material are attributed to the combined effect of processing method and higher Y2O3 content.

  19. Sintering Behavior of Metal Powders Involving Microwave-Enhanced Chemical Reaction

    NASA Astrophysics Data System (ADS)

    Takayama, Sadatsugu; Saito, Yasushi; Sato, Motoyasu; Nagasaka, Takuya; Muroga, Takeo; Ninomiya, Yoshihiko

    2006-03-01

    Copper powder compacts were sintered by microwave radiation in air. In this procedure, the samples were sintered by microwave in air without using any special atmosphere, only by protecting them in a container filled with ceramic powder. The enhancement of the deoxidation reaction by the microwave was observed. The samples were analyzed by using scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD) analysis. The samples were deoxidized on the surface and were well sintered to the edge from the inside throughout the entire cross section. The tensile strength of the copper samples sintered by the microwave in air was higher than that found in conventional sintering in N2 gas. No other differences were noticed between the samples sintered by the microwave under the air-rich conditions and in the conventional furnace in H2+N2 gas. The microwave-sintered copper samples were of good quality; for example, the tensile strength measured throughout the cross section was the same as that for the samples sintered in H2+N2 gas by the conventional method.

  20. Sintered reaction bonded Si3N4 for the AGT 101 turbine rotor

    NASA Technical Reports Server (NTRS)

    Mangels, J. A.

    1980-01-01

    The sintered reaction reaction bonded Si3N4 (SRBSN) process, with Y2O3 as a sintering aid, was selected for the fabrication of the AGT 101 turbine rotor. Experiments to determine the optimum Y2O3 composition of this system are discussed. The room temperature strength of the optimum material (RM-1) exceeds 700 MPa while the 1200 C strength exceeds 550 MPa. The slip casting fabrication technique employed for the AGT 101 simulated rotor is described. Rotors have been cast, nitrided and sintered. Densities exceeding 97% of theoretical (3.26 g/cc) have been obtained. Problems relating to sintering reproducibility, and the overall quality of the simulated rotors have been identified.

  1. A novel sintering method to obtain fully dense gadolinia doped ceria by applying a direct current

    NASA Astrophysics Data System (ADS)

    Hao, Xiaoming; Liu, Yajie; Wang, Zhenhua; Qiao, Jinshuo; Sun, Kening

    2012-07-01

    A fully dense Ce0.8Gd0.2O1.9 (gadolinia doped ceria, GDC) is obtained by a novel using a sintering technique for several seconds at 545 °C by applying a direct current (DC) electrical field of 70 V cm-1. The onset applied field value of this phenomenon is 20 V cm-1, and the volume specific power dissipation for the onset of flash sintering is about ∼10 mW mm-3. Through contrast with the shrinkage strain of the conventional sintering as well as scanning electron microscopy (SEM) analysis, we conclude that GDC specimens are sintered to fully density under various applied fields. In addition, we demonstrate that the grain size of GDC is decreasing with the increase of applied field and the decrease of sintering temperature. Through calculation, we find that sintering of GDC can be explained by the Joule heating from the applied electrical field.

  2. Hot isostatic pressing of direct selective laser sintered metal components

    NASA Astrophysics Data System (ADS)

    Wohlert, Martin Steven

    2000-10-01

    A new manufacturing process combining the benefits of Selective Laser Sintering (SLS) and Hot Isostatic Pressing (HIP) has been developed to permit Rapid Prototyping of high performance metal components. The new process uses Direct Metal SLS to produce a gas impermeable HIP container from the same powdered material that will eventually compose the bulk of the part. The SLS generated capsule performs the functions of the sheet metal container in traditional HIP, but unlike a sheet metal container, the SLSed capsule becomes an integral part of the final component. Additionally, SLS can produce a capsule of far greater geometric complexity than can be achieved by sheet metal forming. Two high performance alloys, Ti-6Al-4V and Inconel 625, were selected for use in the development of the new process. HIP maps were constructed to predict the densification rate of the two materials during HIP processing. Comparison to experimentally determined densification behavior indicated that the maps provide a useful qualitative description of densification rates; however, the accuracy of quantitative predictions was greatly enhanced by tuning key material parameters based on a limited number of experimental HIP cycles. Microstructural characterization of SLS + HIP samples revealed two distinct regions within the components. The outer SLS processed capsule material exhibited a relatively coarse microstructure comparable to a cast, or multi-layer welded structure. No layer boundaries were discernible in the SLS material, with grains observed to grow epitaxially from previously deposited material. The microstructure of the HIP consolidated core material was similar to conventionally HIP processed powder materials, featuring a fine grain structure and preserved prior particle boundaries. The large variation in grain size between the capsule and core materials was reflected in hardness measurements conducted on the Alloy 625 material; however, the variation in hardness was less

  3. Sintering behavior of ultrafine silicon carbide powders obtained by vapor phase reaction

    NASA Technical Reports Server (NTRS)

    Okabe, Y.; Miyachi, K.; Hojo, J.; Kato, A.

    1984-01-01

    The sintering behavior of ultrafine SiC powder with average particle size of about 0.01-0.06 microns produced by a vapor phase reaction of the Me4Si-H2 system was studied at the temperature range of 1400-2050 deg. It was found that the homogeneous dispersion of C on SiC particles is important to remove the surface oxide layer effectively. B and C and inhibitive effect on SiC grain growth.

  4. Fracture of flash oxidized, yttria-doped sintered reaction-bonded silicon nitride

    NASA Technical Reports Server (NTRS)

    Govila, R. K.

    1987-01-01

    The oxidation behavior of a slip cast, yttria-doped, sintered reaction-bonded silicon nitride after 'flash oxidation' was investigated. It was found that both the static oxidation resistance and flexural stress rupture life (creep deformation) were improved at 1000 C in air compared to those of the same material without flash oxidation. Stress rupture data at high temperatures (1000 to 1200 C) are presented to indicate applied stress levels for oxidation-dependent and independent failures.

  5. Gelcasting of silicon preforms for the production of sintered reaction-bonded silicon nitride

    SciTech Connect

    Kiggans, J.O. Jr.; Nunn, S.D.; Tiegs, T.N.; Davisson, C.C.; Coffey, D.W.; Maria, J.P.

    1995-12-31

    Gelcasting of silicon metal for the production of sintered reaction-bonded silicon nitride (SRBSN) was investigated in order to identify associated advantages over conventional forming techniques, i.e., die and isostatic pressing. Compacts were formed from identical powder mixtures by both gelcasting and pressing, and were nitrided and sintered to produce SRBSN ceramics using both conventional and microwave heating. Characterization of the samples included measurement of green density, green and nitrided pore structure, weight gain during nitridation, final density, microstructure, toughness, and flexural strength. It was found that a more uniform pore structure existed in the green gelcast samples. It is believed that this pore configuration aided in nitridation, and manifested itself in a more uniform final microstructure. In addition, improved mechanical properties were achieved in the gelcast samples. This improvement can be attributed to green microstructure homogeneity. An additional finding of this study was that microwave hearing combined with gelcast forming resulted in SRBSN materials with improved mechanical properties.

  6. Effect of composition on the processing and properties of sintered reaction-bonded silicon nitride

    SciTech Connect

    Tiegs, T.N.; Kiggans, J.O.; Montgomery, F.C.; Lin, H.T.; Barker, D.L.; Snodgrass, J.D.; Sabolsky, E.M.; Coffey, D.W.

    1996-04-01

    The type of silicon powder and sintering additive were found to influence the processing and final mechanical properties of sintered reaction bonded silicon nitride. High purity silicon powders produced low {alpha}-Si{sub 3}N{sub 4} content during nitridation. The Si powder type had no apparent effect on densification. More complete nitridation and higher room temperature mechanical properties were observed for the Si powders with higher Fe contents. However, the higher Fe contents resulted in greater high temperature strength degradation and so there was better high temperature strength retention with the higher purity Si. High {alpha}-Si{sub 3}N{sub 4} contents were found after nitridation with {alpha}-Si{sub 3}N{sub 4} seeded materials and with MgO-Y{sub 2}O{sub 3} as the sintering additive. Densification was inhibited by refractory additives, such as Y{sub 2}O{sub 3}-SiO{sub 2}. The highest room temperature strength and fracture toughness values correlated to high nitrided {alpha}-Si{sub 3}N{sub 4} contents. The high temperature strength behavior was similar for all additive types.

  7. Effect of Sintering Temperature on Electrical Properties of Chip on Glass Module with Direct Printing Method

    NASA Astrophysics Data System (ADS)

    Lee, Young-Chul; Kim, Yongil; Jung, Seung-Boo

    2012-09-01

    In order to apply the direct printing method to the fabrication of chip on glass (COG) modules, we examined that the effect of the sintering temperature on the electrical properties of a COG module with direct printing method. Firstly, we fabricated an Ag conductive circuit on a glass substrate by the screen-printing method. To investigate its the effect on the electrical properties of the circuit, it was sintered at various temperatures, such as 150, 200, 250, and 300 °C for 30 min. Subsequently, we conducted Au electro-plating for the fabrication of a Si dummy chip. Finally, the flip-chip bonding process was conducted using anisotropic conductive film (ACF). The printed Ag circuits were well formed on the quartz substrate without any shorts or remarkable changes compared with the initial design. The electrical properties of the printed Ag circuits improved with increasing sintering temperature. The conductive particles in the ACF were well deformed in between the Au bumps and printed Ag pads after the bonding process. The four-point probe method was employed to measure the connection resistance of the joints constructed with the Au bumps on the Si chip and printed Ag circuit on the quartz substrate. The resistances of the interconnections drastically decreased with increasing sintering temperature, i.e., subsequently converged from 11.8 Ω to 7.36 mΩ.

  8. Chemical sintering of direct-written silver nanowire flexible electrodes under room temperature

    NASA Astrophysics Data System (ADS)

    Hui, Zhuang; Liu, Yangai; Guo, Wei; Li, Lihang; Mu, Nan; Jin, Chao; Zhu, Ying; Peng, Peng

    2017-07-01

    Transparent and flexible electrodes on cost effective plastic substrates for wearable electronics have attract great attention recently. Due to the conductivity and flexibility in network form, metal nanowire is regarded as one of the most promising candidates for flexible electrode fabrication. Prior to application, low temperature joining of nanowire processes are required to reduce the resistance of electrodes and simultaneously maintain the dimensionality and uniformity of those nanowires. In the present work, we presented an innovative, robust and cost effective method to minimize the heat effect to plastic substrate and silver nanowires which allows silver nanowire electrodes been directly written on polycarbonate substrate and sintered by different electrolyte solutions at room temperature or near. It has been rigorously demonstrated that the resistance of silver nanowire electrodes has been reduced by 90% after chemical sintering at room temperature due to the joining of silver nanowires at junction areas. After ∼1000 bending cycles, the measured resistance of silver nanowire electrode was stable during both up-bending and down-bending states. The changes of silver nanowires after sintering were characterized using x-ray photoelectron spectroscopy and transmission electron microscopy and a sintering mechanism was proposed and validated. This direct-written silver nanowire electrode with good performance has broad applications in flexible electronics fabrication and packaging.

  9. Fracture of yttria-doped, sintered reaction-bonded silicon nitride

    NASA Technical Reports Server (NTRS)

    Govila, R. K.; Mangels, J. A.; Baer, J. R.

    1985-01-01

    Flexural strength of an yttria-doped, slip-cast, sintered reaction-bonded silicon nitride was evaluated as a function of temperature (20 to 1400 C in air), applied stress, and time. Static oxidation at 700 to 1400 C was investigated in detail; in tests at 1000 C in air, the material showed anomalous weight gain. Flexural stress-rupture testing at 800 to 1200 C in air indicated that the material is susceptible to stress-enhanced oxidation and early failure. Fractographic evidence for time-dependent and -independent failures is presented.

  10. Fracture of yttria-doped, sintered reaction-bonded silicon nitride

    NASA Technical Reports Server (NTRS)

    Govila, R. K.; Mangels, J. A.; Baer, J. R.

    1985-01-01

    Flexural strength of an yttria-doped, slip-cast, sintered reaction-bonded silicon nitride was evaluated as a function of temperature (20 to 1400 C in air), applied stress, and time. Static oxidation at 700 to 1400 C was investigated in detail; in tests at 1000 C in air, the material showed anomalous weight gain. Flexural stress-rupture testing at 800 to 1200 C in air indicated that the material is susceptible to stress-enhanced oxidation and early failure. Fractographic evidence for time-dependent and -independent failures is presented.

  11. Effect of Oxidation on the Densification of Sinterable RBSN (Reaction-Bonded Silicon Nitride).

    DTIC Science & Technology

    1986-01-01

    pressure/temperature cycle. Some bars were preoxidized at 10000C prior to sintering to increase the oxygen content (SiO2 ) of the speci- - mens and...tering process. Those kinetics are influenced by the amount and stability of each component or compound formed and the reaction path. Additionally...yttrium-nitrogen apatite (Y5Si301 2N) with a small amount of free silicon also detected. The densities of the specimens were between 2.4 and 2.5 g/cc

  12. Sintered reaction bonded Si/sub 3/N/sub 4/ for the AGT 101 turbine rotor

    SciTech Connect

    Mangels, J.A.

    1980-01-01

    The sintered reaction bonded Si/sub 3/N/sub 4/ (SRBSN) process, with Y/sub 2/O/sub 3/ as a sintering aid, was selected for the fabrication of the AGT 101 turbine rotor. Experiments to determine the optimum Y/sub 2/O/sub 3/ composition of this system are discussed. The room temperature strength of the optimum material (RM-1) exceeds 700 MPa while the 1200 C strength exceeds 550 MPa. The slip casting fabrication technique employed for the AGT 101 simulated rotor is described. Rotors have been cast, nitrided and sintered. Densities exceeding 97% of theoretical (3.26 g/cc) have been obtained. Problems relating to sintering reproducibility, and the overall quality of the simulated rotors have been identified.

  13. Improved reaction sintered silicon nitride. [protective coatings to improve oxidation resistance

    NASA Technical Reports Server (NTRS)

    Baumgartner, H. R.

    1978-01-01

    Processing treatments were applied to as-nitrided reaction sintered silicon nitride (RSSN) with the purposes of improving strength after processing to above 350 MN/m2 and improving strength after oxidation exposure. The experimental approaches are divided into three broad classifications: sintering of surface-applied powders; impregnation of solution followed by further thermal processing; and infiltration of molten silicon and subsequent carburization or nitridation of the silicon. The impregnation of RSSN with solutions of aluminum nitrate and zirconyl chloride, followed by heating at 1400-1500 C in a nitrogen atmosphere containing silicon monoxide, improved RSSN strength and oxidation resistance. The room temperature bend strength of RSSN was increased nearly fifty percent above the untreated strength with mean absolute strengths up to 420 MN/m2. Strengths of treated samples that were measured after a 12 hour oxidation exposure in air were up to 90 percent of the original as-nitrided strength, as compared to retained strengths in the range of 35 to 60 percent for untreated RSSN after the same oxidation exposure.

  14. Preparation and Characterization of (Mo, W)Si2-SiC Composites by In Situ Microwave Reaction Sintering

    NASA Astrophysics Data System (ADS)

    Wu, Haijiang; Chen, Fang; Xu, Jianguang

    2017-07-01

    MoSi2-based materials are considered potentially useful for making high-temperature structural parts. In this work, (Mo, W)Si2-SiC composites have been successfully prepared in situ by microwave reaction sintering of the elemental reactants. Benefiting from the lower sintering temperature and faster densification procedure, the as-prepared composites have finer microstructures compared to the analogs prepared by conventional reaction sintering, resulting in a significant improvement of mechanical properties. The flexural strength, Vickers hardness and fracture toughness of 10%SiC/10%WSi2/80%MoSi2 are as high as 302.81 MPa, 8.55 GPa and 8.90 MPa m1/2, respectively, which are also better than those of monolithic MoSi2 and 10%SiC/90%MoSi2 composite due to the synergistic strengthening and toughening effects of W alloying and SiC second phase.

  15. Controlled metal-semiconductor sintering/alloying by one-directional reverse illumination

    DOEpatents

    Sopori, Bhushan L.

    1993-01-01

    Metal strips deposited on a top surface of a semiconductor substrate are sintered at one temperature simultaneously with alloying a metal layer on the bottom surface at a second, higher temperature. This simultaneous sintering of metal strips and alloying a metal layer on opposite surfaces of the substrate at different temperatures is accomplished by directing infrared radiation through the top surface to the interface of the bottom surface with the metal layer where the radiation is absorbed to create a primary hot zone with a temperature high enough to melt and alloy the metal layer with the bottom surface of the substrate. Secondary heat effects, including heat conducted through the substrate from the primary hot zone and heat created by infrared radiation reflected from the metal layer to the metal strips, as well as heat created from some primary absorption by the metal strips, combine to create secondary hot zones at the interfaces of the metal strips with the top surface of the substrate. These secondary hot zones are not as hot as the primary hot zone, but they are hot enough to sinter the metal strips to the substrate.

  16. Thermochemical analysis of the silicon carbide-alumina reaction with reference to liquid-phase sintering of silicon carbide

    NASA Technical Reports Server (NTRS)

    Misra, Ajay K.

    1991-01-01

    The stabilities of different phases in the Si-Al-C-O system are calculated from thermodynamic considerations with the objective of identifying the liquid phases formed during sintering of SiC in the presence of Al2O3. It is shown that a liquid phase can form at the sintering temperatures by the reaction of SiC with Al2O3. Depending on the carbon activity, the liquid can be either of the following: Al2O3 + Al4C3, SiC + Al4C3, or molten aluminum. The stability of the aluminosilicate melts that can form by the reaction of Al2O3 with the surface silica layer on SiC powders is also evaluated. Several factors that influence liquid-phase sintering, such as the solubility of SiC in the melts and the generation of gases during sintering, are discussed. The results of the thermodynamic analysis are compared with the observed sintering behavior for SiC.

  17. Fabrication and evaluation of solid-oxide fuel cell anodes employing reaction-sintered yttria-stabilized zirconia

    NASA Astrophysics Data System (ADS)

    Storjohann, Daniel; Daggett, James; Sullivan, Neal P.; Zhu, Huayang; Kee, Robert J.; Menzer, Sophie; Beeaff, Dustin

    This paper reports on the fabrication and performance of solid-oxide fuel cell (SOFC) anodes utilizing yttria reaction-sintered zirconia (YRSZ). Through the reaction-sintering process, the technical-grade YSZ commonly used in the Ni-YSZ anode cermet is replaced with lower-cost ZrO 2 and Y 2O 3 materials. When sintered in the presence of nickel oxide, ZrO 2 and Y 2O 3 form cubic-phase YSZ at temperatures characteristic of SOFC processing (1400-1550 ° C). Reaction sintering enables the formation of YSZ during cell fabrication, reducing SOFC anode raw-materials cost and the number of SOFC-fabrication processes. This paper reports the results of a broad range of characterization and performance measurements to evaluate the YRSZ material, including (1) crystal structure, (2) morphology, (3) pore-size distribution, (4) electronic resistivity, (5) fracture strength, (6) gas transport and catalytic activity, and (7) electrochemical performance. Material properties and performance are found to be comparable to or better than equivalent materials fabricated by conventional processes.

  18. Controlling Directed Self-Assembly and Sintering of Gold Nanorods in Patterned Block Copolymer Thin Films

    NASA Astrophysics Data System (ADS)

    Lai, Fengyuan

    As the miniaturization of electronic devices continues, proper thermal management is crucial to ensure the optimum performance and reliability of such devices within their specification. Of primary interest are the so-called thermal interface materials to minimize the thermal resistance between the heat source and the heat sink. To this end, polymer nanocomposites composed of a polymer matrix and nanoscale fillers with high thermal conductivity have attracted tremendous attention. It has been demonstrated that the formation of a nanoparticle assembly inside the polymer matrix provides a continuous pathway for efficient heat transfer, and thus it is essential for achieving high thermal conductivity. In this work, we explored the ability to direct the self-assembly of gold nanorods (AuNRs) via patterned block copolymer (BCP) thin films. Selective sequestration of AuNRs with various aspect ratios in one block domain was achieved, with over 30% of the surface covered by an ordered AuNR assembly orienting parallel to the geometric confinement. The final nanostructure resulting from the directed self-assembly process is determined by the competition between thermodynamic consideration and kinetic factors. The coalescence and sintering of the AuNR assembly was accomplished by both furnace thermal annealing and rapid thermal annealing at low temperatures. The mechanism through which efficient sintering occurred is investigated with scanning electron microscopy. It is found that the sintering process initially takes place locally, resulting in small AuNR aggregates. Eventually the aggregates grow into a globally continuous, percolating network structure. In addition, the overall heat transfer coefficient was measured in an environmental scanning electron microscope by following droplet growth over time. The present study opens up new opportunities to accomplish controlled assembly of nanoparticles with high concentration for different nanorod-based applications as well as

  19. Enhancement of thermal shock resistance of reaction sintered mullite–zirconia composites in the presence of lanthanum oxide

    SciTech Connect

    Kumar, P.; Nath, M.; Ghosh, A.; Tripathi, H.S.

    2015-03-15

    Mullite–zirconia composites containing 20 wt.% zirconia were prepared by reaction sintering of zircon flour, sillimanite beach sand and calcined alumina. 0 to 8 mol% of La{sub 2}O{sub 3} with respect to zirconia was used as sintering aid. The effect of additive on the various physical, microstructures, mechanical and thermo-mechanical properties was studied. Quantitative phase analysis shows the change in tetragonal zirconia content with incorporation of lanthanum oxide. La{sub 2}O{sub 3} addition has significantly improved the thermal shock resistance of the samples. Samples without additive retained only 20% of initial flexural strength after 5 cycles, whereas samples containing 5 mol% La{sub 2}O{sub 3} retained almost 78% of its initial flexural strength even after 15 thermal shock cycles. - Highlights: • Mullite–zirconia composites were prepared by reaction sintering route utilizing zircon and sillimanite beach sand. • Lanthanum oxide was used as sintering aid. • The presence of lanthanum oxide decreased the densification temperature. • Lanthanum oxide significantly improved the thermal shock resistance of the composites.

  20. Direct Selective Laser Sintering/Melting of High Density Alumina Powder Layers at Elevated Temperatures

    NASA Astrophysics Data System (ADS)

    Deckers, J.; Meyers, S.; Kruth, J. P.; Vleugels, J.

    Direct selective laser sintering (SLS) or selective laser melting (SLM) are additive manufacturing techniques that can be used to produce three-dimensional ceramic parts directly, without the need for a sacrificial binder. In this paper, a low laser energy density is applied to SLS/SLM high density powder layers of sub-micrometer alumina at elevated temperatures (up to 800̊C). In order to achieve this, a furnace was designed and built into a commercial SLS machine. This furnace was able to produce a homogeneously heated cylindrical zone with a height of 60 mm and a diameter of 32 mm. After optimizing the layer deposition and laser scanning parameters, two ceramic parts with a density up to 85% and grain sizes as low as 5 μm were successfully produced.

  1. Direct selective laser sintering of high performance metals: Machine design, process development and process control

    NASA Astrophysics Data System (ADS)

    Das, Suman

    1998-11-01

    This dissertation describes the development of an advanced manufacturing technology known as Direct Selective Laser Sintering (Direct SLS). Direct SLS is a laser based rapid manufacturing technology that enables production of functional, fully dense, metal and cermet components via the direct, layerwise consolidation of constituent powders. Specifically, this dissertation focuses on a new, hybrid net shape manufacturing technique known as Selective Laser Sintering/Hot Isostatic Pressing (SLS/HIP). The objective of research presented in this dissertation was to establish the fundamental machine technology and processing science to enable direct SLS fabrication of metal components composed of high performance, high temperature metals and alloys. Several processing requirements differentiate direct SLS of metals from SLS of polymers or polymer coated powders. Perhaps the most important distinguishing characteristic is the regime of high temperatures involved in direct SLS of metals. Biasing the temperature of the feedstock powder via radiant preheat prior to and during SLS processing was shown to be beneficial. Preheating the powder significantly influenced the flow and wetting characteristics of the melt. During this work, it was conclusively established that powder cleanliness is of paramount importance for successful layerwise consolidation of metal powders by direct SLS. Sequential trials were conducted to establish optimal bake-out and degas cycles under high vacuum. These cycles agreed well with established practices in the powder metallurgy industry. A study of some of the important transport mechanisms in direct SLS of metals was undertaken to obtain a fundamental understanding of the underlying process physics. This study not only provides an explanation of phenomena observed during SLS processing of a variety of metallic materials but also helps in developing selection schemes for those materials that are most amenable to direct SLS processing. The

  2. Metallurgical and Mechanical Evaluation of 4340 Steel Produced by Direct Metal Laser Sintering

    NASA Astrophysics Data System (ADS)

    Jelis, Elias; Clemente, Matthew; Kerwien, Stacey; Ravindra, Nuggehalli M.; Hespos, Michael R.

    2015-03-01

    Direct metal laser sintering (DMLS) was used to produce high-strength low-alloy 4340 steel specimens. Mechanical and metallurgical analyses were performed on the specimens to determine the samples with the highest strengths and the least porosity. The optimal process parameters were thus defined based on the corresponding experimental conditions. Additionally, the effects of fabricating specimens with both virgin and recycled powders were studied. Scanning electron microscopy and electron-dispersive spectroscopy were performed on both types of powders to determine the starting morphology and composition. The initial tensile results are promising, suggesting that DMLS can produce specimens equal in strength to wrought materials. However, there is evidence of cracking on several of the heat-treated tensile specimens that is unexplained. Several theories point to disturbances in the build chamber environment that went undetected while the specimens were being fabricated.

  3. Nondestructive Evaluation of the J-2X Direct Metal Laser Sintered Gas Generator Discharge Duct

    NASA Technical Reports Server (NTRS)

    Esther, Elizabeth A.; Beshears, Ronald D.; Lash, Rhonda K.

    2012-01-01

    The J-2X program at NASA's Marshall Space Flight Center (MSFC) procured a direct metal laser sintered (DMLS) gas generator discharge duct from Pratt & Whitney Rocketdyne and Morris Technologies for a test program that would evaluate the material properties and durability of the duct in an engine-like environment. DMLS technology was pursued as a manufacturing alternative to traditional techniques, which used off nominal practices to manufacture the gas generator duct's 180 degree turn geometry. MSFC's Nondestructive Evaluation (NDE) Team performed radiographic, ultrasonic, computed tomographic, and fluorescent penetrant examinations of the duct. Results from the NDE examinations reveal some shallow porosity but no major defects in the as-manufactured material. NDE examinations were also performed after hot-fire testing the gas generator duct and yielded similar results pre and post-test and showed no flaw growth or development.

  4. Fabrication of water-cooled laser silicon mirror by direct laser sintering.

    PubMed

    He, Chongwen; Zhu, Haihong; Hu, Panpan

    2014-04-21

    Coppery heat sink with micro pores and Sub-millimeter channel has been fabricated by direct laser sintering on the back of the silicon mirror. To verify the heat dissipation capability of the fabricated heat sink, a Twyman-Green interferometer was employed to measure the thermal deformation of the silicon mirror radiated by a high power laser. It is shown that the thermal deformation of the mirror increases with the irradiating time and laser intensity. The heat balance can be achieved after several seconds of laser irradiation even when the net absorbed laser power density is up to 5.3 × 10(5) W/m(2). The time for reaching the heat balance also increases with the laser intensity. The maximum thermal deformation of the mirror is 0.65 µm if the net absorbed laser power density is 5.3 × 10(5) W/m(2).

  5. Corrosion of Ti6Al4V pins produced by direct metal laser sintering

    NASA Astrophysics Data System (ADS)

    de Damborenea, J. J.; Arenas, M. A.; Larosa, Maria Aparecida; Jardini, André Luiz; de Carvalho Zavaglia, Cecília Amélia; Conde, A.

    2017-01-01

    Direct Metal Laser Sintering (DMLS) technique allows the manufacturing a wide variety of medical devices for any type of prosthetic surgery (HIP, dental, cranial, maxillofacial) as well as for internal fixation devices (K-Wires or Steinmann Pins). There are a large number of research studies on DMLS, including microstructural characterization, mechanical properties and those based on production quality assurance but the influence of porosity in the corrosion behavior of these materials not been sufficiently considered. In the present paper, surgical pins of Ti6Al4V have been produced by DMLS. After testing in a phosphate buffered saline solution, the surface of the titanium alloy appeared locally covered by a voluminous white oxide. This unexpected behavior was presumably due to the existence of internal defects in the pins as result of the manufacturing process. The importance of these defects-that might act as crevice nucleation sites- has been revealed by electrochemical techniques and confirmed by computed tomography.

  6. Reaction of Unalloyed and Cr-Mo Alloyed Steels with Nitrogen from the Sintering Atmosphere

    NASA Astrophysics Data System (ADS)

    Dlapka, Magdalena; Gierl-Mayer, Christian; Calderon, Raquel de Oro; Danninger, Herbert; Bengtsson, Sven; Dudrova, Eva

    2016-12-01

    Nitrogen is usually regarded as an inert sintering atmosphere for PM steels; however, this cannot be taken for granted in particular for steels alloyed with nitride forming elements. Among those elements, chromium has become more and more important as an alloying element in sintered low alloy structural steels in the last decade due to the moderate alloying cost and the excellent mechanical properties obtainable, in particular when sinter hardening is applied. The high affinity of Cr to oxygen and the possible ways to overcome related problems have been the subject of numerous studies, while the fact that chromium is also a fairly strong nitride forming element has largely been neglected at least for low alloy steel grades, although frequently used materials like steels from Cr and Cr-Mo prealloyed powders are commonly sintered in atmospheres consisting mainly of nitrogen. In the present study, nitrogen pickup during sintering at different temperatures and for varying times has been studied for Cr-Mo prealloyed steel grades as well as for unalloyed carbon steel. Also the effect of the cooling rate and its influence on the properties, of the microstructure and the composition have been investigated. It showed that the main nitrogen uptake occurs not during isothermal sintering but rather during cooling. It could be demonstrated that a critical temperature range exists within which the investigated CrM-based steel is particularly sensitive to nitrogen pickup.

  7. Modeling of microstructure evolution in direct metal laser sintering: A phase field approach

    NASA Astrophysics Data System (ADS)

    Nandy, Jyotirmoy; Sarangi, Hrushikesh; Sahoo, Seshadev

    2017-02-01

    Direct Metal Laser Sintering (DMLS) is a new technology in the field of additive manufacturing, which builds metal parts in a layer by layer fashion directly from the powder bed. The process occurs within a very short time period with rapid solidification rate. Slight variations in the process parameters may cause enormous change in the final build parts. The physical and mechanical properties of the final build parts are dependent on the solidification rate which directly affects the microstructure of the material. Thus, the evolving of microstructure plays a vital role in the process parameters optimization. Nowadays, the increase in computational power allows for direct simulations of microstructures during materials processing for specific manufacturing conditions. In this study, modeling of microstructure evolution of Al-Si-10Mg powder in DMLS process was carried out by using a phase field approach. A MATLAB code was developed to solve the set of phase field equations, where simulation parameters include temperature gradient, laser scan speed and laser power. The effects of temperature gradient on microstructure evolution were studied and found that with increase in temperature gradient, the dendritic tip grows at a faster rate.

  8. Reaction sintering of two-dimensional silicon carbide fiber-reinforced silicon carbide composite by sheet stacking method

    NASA Astrophysics Data System (ADS)

    Yoshida, Katsumi; Mukai, Hideki; Imai, Masamitsu; Hashimoto, Kazuaki; Toda, Yoshitomo; Hyuga, Hideki; Kondo, Naoki; Kita, Hideki; Yano, Toyohiko

    2007-08-01

    Two-dimensionally plain woven SiC fiber-reinforced SiC composite has been developed by reaction sintering using a sheet stacking method in order to further increase mechanical and thermal properties of the composite and to obtain flexibility of manufacturing process of 2D woven SiC/SiC composites which can be applied to the fabrication of larger parts. In addition, sinterability and mechanical properties of the composite were investigated. In this study, relative density of the composites was about 90-93% and a dense composite could be obtained by reaction sintering using the sheet stacking method. The bulk density and maximum bending strength of SiC/SiC composite with a C/SiC weight ratio of 0.6 were higher than that of the composite with C/SiC ratios of 0.5 or 0.7. The values were 2.9 g/cm 3 and 200 MPa, respectively. However, the composites obtained in this study fractured in almost brittle manner due to the lower fiber volume fraction.

  9. Interfacial reactions and wetting in Al-Mg sintered by powder metallurgy process

    SciTech Connect

    Faisal, Heny Darminto,; Triwikantoro,; Zainuri, M.

    2016-04-19

    Was conducted to analyze the effect of temperature variation on the bonding interface sintered composite Al-Mg and analyze the effect of variations of the density and hardness sinter. Research carried out by the base material powders of Al, Mg powder and solvent n-butanol. The method used in this study is a powder metallurgy, with a composition of 60% volume fraction of Al - 40% Mg. Al-Mg mixing with n-butanol for 1 hour at 500 rpm. Then the emphasis (cold comression) with a size of 1.4 cm in diameter dies and height of 2.8 cm, is pressed with a force of 20 MPa and held for 15 minutes. After the sample into pellets, then sintered at various temperatures 300 °C, 350 °C, 400 °C and 450 °C. Characterization is done by using the testing green density, sintered density, X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), vickers microhardness, and press test. XRD data analysis done by using X’Pert High Score Plus (HSP) to determine whether there is a new phase is formed. Test results show that the sintered density increasing sintering temperature, the resulting density is also increasing (shrinkage). However, at a temperature of 450 °C decreased (swelling). With the increased sinter density, interfacial bonding getting Kuta and more compact so that its hardness is also increased. From the test results of SEM / EDX, there Mg into Al in the border area. At temperatures of 300 °C, 350 °C, 400 °C, the phase formed is Al, Mg and MgO. While phase is formed at a temperature of 450 °C is aluminum magnesium (Al{sub 3}Mg{sub 2}), Aluminum Magnesium Zinc (AlMg{sub 2}Zn).

  10. The Direct Catalytic Asymmetric Aldol Reaction

    PubMed Central

    Brindle, Cheyenne S.

    2013-01-01

    Asymmetric aldol reactions are a powerful method for the construction of carbon-carbon bonds in an enantioselective fashion. Historically this reaction has been performed in a stoichiometric fashion to control the various aspects of chemo-, diastereo-, regio- and enantioselectivity, however, a more atom economical approach would unite high selectivity with the use of only a catalytic amount of a chiral promoter. This critical review documents the development of direct catalytic asymmetric aldol methodologies, including organocatalytic and metal-based strategies. New methods have improved the reactivity, selectivity and substrate scope of the direct aldol reaction and enabled the synthesis of complex molecular targets PMID:20419212

  11. Influence of phosphorus element on direct laser sintering of multicomponent Cu-based metal powder

    NASA Astrophysics Data System (ADS)

    Gu, D. D.; Shen, Y. F.

    2006-12-01

    This article presents a detailed investigation on the influence of the phosphorus element upon the laser sintering of a multicomponent Cu-based metal powder system consisting of Cu, Cu-10Sn, and Cu-8.4P. Powder systems containing 0, 10, 15, and 20 wt pct CuP were sintered in atmosphere at room temperature using the following optimal processing parameters: laser power of 350 W, scan speed of 0.04 m/s, scan line spacing of 0.15 mm, and layer thickness of 0.25 mm. It was found that the relative density of the sintered sample with 15 wt pct CuP increased by 24,4 pct as compared with the sample without phosphorus addition. A further increase in the CuP content (≥20 wt pct), however, resulted in a poor densification with a serious delamination. The exact metallurgical roles of the phosphorus element in the laser sintering process were addressed as follows. First, the phosphorus could prevent the sintering system from oxidation by forming CuPO3, thereby improving the wetting characteristics and the sintering kinetics. Second, the phosphorus could decrease the surface tension of molten materials, leading to a successive transition from highly discontinuous sintered tracks to fairly coherent ones with increasing the phosphorus content. Third, the phosphorus could lower the melt viscosity, thereby improving the microstructural homogeneity of the laser-sintered samples.

  12. Mechanical properties of thermoelectric n-type magnesium silicide synthesized employing in situ spark plasma reaction sintering

    NASA Astrophysics Data System (ADS)

    Muthiah, Saravanan; Singh, R. C.; Pathak, B. D.; Dhar, Ajay

    2017-07-01

    Thermoelectric devices employing magnesium silicide (Mg2Si) offer an inexpensive and non-toxic solution for green energy generation compared to other existing conventional thermoelectric materials in the mid-temperature range. However, apart from the thermoelectric performance, their mechanical properties are equally important in order to avoid the catastrophic failure of their modules during actual operation. In the present study, we report the synthesis of Mg2Si co-doped with Bi and Sb employing in situ spark plasma reaction sintering and investigate its broad range of mechanical properties. The mechanical properties of the sintered co-doped Mg2Si suggest a significantly enhanced value of hardness ~5.4  ±  0.2 GPa and an elastic modulus ~142.5  ±  6 GPa with a fracture toughness of ~1.71  ±  0.1 MPa  √m. The thermal shock resistance, which is one of the most vital parameter for designing thermoelectric devices, was found to be ~300 W m-1, which is higher than most of the other existing state-of-the-art mid-temperature thermoelectric materials. The friction and wear characteristics of sintered co-doped Mg2Si have been reported for the first time, in order to realize the sustainability of their thermoelectric modules under actual hostile environmental conditions.

  13. Densification of Reaction Bonded Silicon Nitride with the Addition of Fine Si Powder Effects on the Sinterability and Mechanical Properties

    SciTech Connect

    Lee, Sea-Hoon; Cho, Chun-Rae; Park, Young-Jo; Ko, Jae-Woong; Kim, Hai-Doo; Lin, Hua-Tay; Becher, Paul F

    2013-01-01

    The densification behavior and strength of sintered reaction bonded silicon nitrides (SRBSN) that contain Lu2O3-SiO2 additives were improved by the addition of fine Si powder. Dense specimens (relative density: 99.5%) were obtained by gas-pressure sintering (GPS) at 1850oC through the addition of fine Si. In contrast, the densification of conventional specimens did not complete at 1950oC. The fine Si decreased the onset temperature of shrinkage and increased the shrinkage rate because the additive helped the compaction of green bodies and induced the formation of fine Si3N4 particles after nitridation and sintering at and above 1600oC. The amount of residual SiO2 within the specimens was not strongly affected by adding fine Si powder because most of the SiO2 layer that had formed on the fine Si particles decomposed during nitridation. The maximum strength and fracture toughness of the specimens were 991 MPa and 8.0 MPa m1/2, respectively.

  14. Microstructure and mechanical behavior of direct metal laser sintered Inconel alloy 718

    SciTech Connect

    Smith, Derek H.; Bicknell, Jonathan; Jorgensen, Luke; Patterson, Brian M.; Cordes, Nikolaus L.; Tsukrov, Igor; Knezevic, Marko

    2016-03-15

    In this paper, we investigate microstructure and quasi-static mechanical behavior of the direct metal laser sintered Inconel 718 superalloy as a function of build direction (BD). The printed material was further processed by annealing and double-aging, hot isostatic pressing (HIP), and machining. We characterize porosity fraction and distribution using micro X-ray computed tomography (μXCT), grain structure and crystallographic texture using electron backscattered diffraction (EBSD), and mechanical response in quasi-static tension and compression using standard mechanical testing at room temperature. Analysis of the μXCT imaging shows that majority of porosity develops in the outer layer of the printed material. However, porosity inside the material is also present. The EBSD measurements reveal formation of columnar grains, which favor < 001 > fiber texture components along the BD. These measurements also show evidence of coarse-grained microstructure present in the samples treated by HIP. Finally, analysis of grain boundaries reveal that HIP results in a large number of annealing twins compared to that in samples that underwent annealing and double-aging. The yield strength varies with the testing direction by approximately 7%, which is governed by a combination of grain morphology and crystallographic texture. In particular, we determine tension–compression asymmetry in the yield stress as well as anisotropy of the material flow during compression. We find that HIP lowers yield stress but improves ductility relative to the annealed and aged material. These results are discussed and critically compared with the data reported for wrought material in the same condition. - Highlights: • Microstructure and mechanical properties of DMLS Inconel 718 are studied in function of build direction. • Inhomogeneity of microstructure in the material in several conditions is quantified by μXCT and EBSD. • Anisotropy and asymmetry in the mechanical response are

  15. In-Situ X-Ray Diffraction Observations of Low Temperature Ag-Nanoink Sintering and High Temperature Eutectic Reaction with Copper

    SciTech Connect

    Elmer, J. W.; Specht, Eliot D

    2012-01-01

    Nanoinks, which contain nm sized metallic particles suspended in an organic dispersant fluid, are finding numerous microelectronic applications. Nanoinks sinter at much lower temperatures than bulk metals due to their high surface area to volume ratio and small radius of curvature, which reduces their melting points significantly below their bulk values. The unusually low melting and sintering temperatures have unique potential for materials joining since their melting points increase dramatically after initial sintering. In this paper Ag nanoink is studied using in-situ synchrotron based x-ray diffraction to follow the kinetics of the initial sintering step by analysis of diffraction patterns, and to directly observe the high remelt temperature of sintered nanoinks. Ag nanoink is further explored as a possible eutectic bonding medium with copper by tracking phase transformations to high temperatures where melting occurs at the Ag-Cu eutectic temperature, demonstrating nanoinks as a viable eutectic bonding medium.

  16. Magnetic field effects on liquid-phase reactive sintering of MnBi

    NASA Astrophysics Data System (ADS)

    Mitsui, Yoshifuru; Abematsu, Ken-ichi; Umetsu, Rie Y.; Takahashi, Kohki; Koyama, Keiichi

    2016-02-01

    Magnetic fields effects on liquid-phase reaction sintering on MnBi were investigated. The liquid-phase reaction was so fast even in a zero field that the fraction of in-field sintered ferromagnetic MnBi phase was independent of the external magnetic field. However, the ferromagnetic MnBi crystals in the in-field sintered sample were oriented along the external magnetic field direction. The Lotgering factor of the in-field sintered sample was 0.99. This result indicated that almost completely anisotropic MnBi phase could be obtained by in-field liquid phase reactive sintering.

  17. The effect of preparation conditions on the structure and mechanical properties of reaction-sintered silicon nitride

    NASA Technical Reports Server (NTRS)

    Heinrich, J.

    1980-01-01

    The microstructure of reaction sintered silicon nitride (RSSN) was changed over a wide range by varying the grain density, grain size of the silicon starting powder, nitriding conditions, and by introducing artificial pores. The influence of single microstructural parameters on mechanical properties like room temperature strength, creep behavior, and resistance to thermal shock was investigated. The essential factors influencing these properties were found to be total porosity, pore size distribution, and the fractions of alpha and beta Si3N4. In view of high temperature engineering applications of RSSN, potentials for optimizing the material's properties by controlled processing are discussed.

  18. Direct Metal Laser Sintering Titanium Dental Implants: A Review of the Current Literature

    PubMed Central

    Mangano, F.; Chambrone, L.; van Noort, R.; Miller, C.; Hatton, P.; Mangano, C.

    2014-01-01

    Statement of Problem. Direct metal laser sintering (DMLS) is a technology that allows fabrication of complex-shaped objects from powder-based materials, according to a three-dimensional (3D) computer model. With DMLS, it is possible to fabricate titanium dental implants with an inherently porous surface, a key property required of implantation devices. Objective. The aim of this review was to evaluate the evidence for the reliability of DMLS titanium dental implants and their clinical and histologic/histomorphometric outcomes, as well as their mechanical properties. Materials and Methods. Electronic database searches were performed. Inclusion criteria were clinical and radiographic studies, histologic/histomorphometric studies in humans and animals, mechanical evaluations, and in vitro cell culture studies on DMLS titanium implants. Meta-analysis could be performed only for randomized controlled trials (RCTs); to evaluate the methodological quality of observational human studies, the Newcastle-Ottawa scale (NOS) was used. Results. Twenty-seven studies were included in this review. No RCTs were found, and meta-analysis could not be performed. The outcomes of observational human studies were assessed using the NOS: these studies showed medium methodological quality. Conclusions. Several studies have demonstrated the potential for the use of DMLS titanium implants. However, further studies that demonstrate the benefits of DMLS implants over conventional implants are needed. PMID:25525434

  19. Structural characterization of biomedical Co-Cr-Mo components produced by direct metal laser sintering.

    PubMed

    Barucca, G; Santecchia, E; Majni, G; Girardin, E; Bassoli, E; Denti, L; Gatto, A; Iuliano, L; Moskalewicz, T; Mengucci, P

    2015-03-01

    Direct metal laser sintering (DMLS) is a technique to manufacture complex functional mechanical parts from a computer-aided design (CAD) model. Usually, the mechanical components produced by this procedure show higher residual porosity and poorer mechanical properties than those obtained by conventional manufacturing techniques. In this work, a Co-Cr-Mo alloy produced by DMLS with a composition suitable for biomedical applications was submitted to hardness measurements and structural characterization. The alloy showed a hardness value remarkably higher than those commonly obtained for the same cast or wrought alloys. In order to clarify the origin of this unexpected result, the sample microstructure was investigated by X-ray diffraction (XRD), electron microscopy (SEM and TEM) and energy dispersive microanalysis (EDX). For the first time, a homogeneous microstructure comprised of an intricate network of thin ε (hcp)-lamellae distributed inside a γ (fcc) phase was observed. The ε-lamellae grown on the {111}γ planes limit the dislocation slip inside the γ (fcc) phase, causing the measured hardness increase. The results suggest possible innovative applications of the DMLS technique to the production of mechanical parts in the medical and dental fields. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. Direct metal laser sintering titanium dental implants: a review of the current literature.

    PubMed

    Mangano, F; Chambrone, L; van Noort, R; Miller, C; Hatton, P; Mangano, C

    2014-01-01

    Statement of Problem. Direct metal laser sintering (DMLS) is a technology that allows fabrication of complex-shaped objects from powder-based materials, according to a three-dimensional (3D) computer model. With DMLS, it is possible to fabricate titanium dental implants with an inherently porous surface, a key property required of implantation devices. Objective. The aim of this review was to evaluate the evidence for the reliability of DMLS titanium dental implants and their clinical and histologic/histomorphometric outcomes, as well as their mechanical properties. Materials and Methods. Electronic database searches were performed. Inclusion criteria were clinical and radiographic studies, histologic/histomorphometric studies in humans and animals, mechanical evaluations, and in vitro cell culture studies on DMLS titanium implants. Meta-analysis could be performed only for randomized controlled trials (RCTs); to evaluate the methodological quality of observational human studies, the Newcastle-Ottawa scale (NOS) was used. Results. Twenty-seven studies were included in this review. No RCTs were found, and meta-analysis could not be performed. The outcomes of observational human studies were assessed using the NOS: these studies showed medium methodological quality. Conclusions. Several studies have demonstrated the potential for the use of DMLS titanium implants. However, further studies that demonstrate the benefits of DMLS implants over conventional implants are needed.

  1. Comparison of residual stresses in Inconel 718 simple parts made by electron beam melting and direct laser metal sintering

    SciTech Connect

    Kolbus, Lindsay M.; Payzant, E. Andrew; Cornwell, Paris A.; Watkins, Thomas R.; Babu, Sudarsanam Suresh; Dehoff, Ryan R.; Duty, Chad E.; Lorenz, M.; Ovchinnikova, O. S.

    2015-01-10

    Residual stress profiles were mapped using neutron diffraction in two simple prism builds of Inconel 718: one fabricated with electron beam melting and the other with direct laser sintering. Spatially indexed stress-free cubes were obtained by EDM sectioning equivalent prisms of similar shape. The (311) interplanar spacing examined for the EDM sectioned sample was compared to the interplanar spacings calculated to fulfill force and moment balance. We have shown that Applying force and moment balance is a necessary supplement to the measurements for the stress-free cubes with respect to accurate stress calculations in additively manufactured components. Furthermore, our work has shown that residual stresses in electron beam melting parts are much smaller than that of direct laser metal sintering parts.

  2. Can the use of pulsed direct current induce oscillation in the applied pressure during spark plasma sintering?

    PubMed Central

    Salamon, David; Eriksson, Mirva; Nygren, Mats; Shen, Zhijian

    2012-01-01

    The spark plasma sintering (SPS) process is known for its rapid densification of metals and ceramics. The mechanism behind this rapid densification has been discussed during the last few decades and is yet uncertain. During our SPS experiments we noticed oscillations in the applied pressure, related to a change in electric current. In this study, we investigated the effect of pulsed electrical current on the applied mechanical pressure and related changes in temperature. We eliminated the effect of sample shrinkage in the SPS setup and used a transparent quartz die allowing direct observation of the sample. We found that the use of pulsed direct electric current in our apparatus induces pressure oscillations with the amplitude depending on the current density. While sintering Ti samples we observed temperature oscillations resulting from pressure oscillations, which we attribute to magnetic forces generated within the SPS apparatus. The described current–pressure–temperature relations might increase understanding of the SPS process. PMID:27877472

  3. Comparison of Residual Stresses in Inconel 718 Simple Parts Made by Electron Beam Melting and Direct Laser Metal Sintering

    NASA Astrophysics Data System (ADS)

    Sochalski-Kolbus, L. M.; Payzant, E. A.; Cornwell, P. A.; Watkins, T. R.; Babu, S. S.; Dehoff, R. R.; Lorenz, M.; Ovchinnikova, O.; Duty, C.

    2015-03-01

    Residual stress profiles were mapped using neutron diffraction in two simple prism builds of Inconel 718: one fabricated with electron beam melting (EBM) and the other with direct laser metal sintering. Spatially indexed stress-free cubes were obtained by electrical discharge machining (EDM) equivalent prisms of similar shape. The (311) interplanar spacings from the EDM sectioned sample were compared to the interplanar spacings calculated to fulfill stress and moment balance. We have shown that applying stress and moment balance is a necessary supplement to the measurements for the stress-free cubes with respect to accurate stress calculations in additively manufactured components. In addition, our work has shown that residual stresses in electron beam melted parts are much smaller than that of direct laser metal sintered parts most likely due to the powder preheating step in the EBM process.

  4. Can the use of pulsed direct current induce oscillation in the applied pressure during spark plasma sintering?

    PubMed

    Salamon, David; Eriksson, Mirva; Nygren, Mats; Shen, Zhijian

    2012-02-01

    The spark plasma sintering (SPS) process is known for its rapid densification of metals and ceramics. The mechanism behind this rapid densification has been discussed during the last few decades and is yet uncertain. During our SPS experiments we noticed oscillations in the applied pressure, related to a change in electric current. In this study, we investigated the effect of pulsed electrical current on the applied mechanical pressure and related changes in temperature. We eliminated the effect of sample shrinkage in the SPS setup and used a transparent quartz die allowing direct observation of the sample. We found that the use of pulsed direct electric current in our apparatus induces pressure oscillations with the amplitude depending on the current density. While sintering Ti samples we observed temperature oscillations resulting from pressure oscillations, which we attribute to magnetic forces generated within the SPS apparatus. The described current-pressure-temperature relations might increase understanding of the SPS process.

  5. Comparison of residual stresses in Inconel 718 simple parts made by electron beam melting and direct laser metal sintering

    DOE PAGES

    Kolbus, Lindsay M.; Payzant, E. Andrew; Cornwell, Paris A.; ...

    2015-01-10

    Residual stress profiles were mapped using neutron diffraction in two simple prism builds of Inconel 718: one fabricated with electron beam melting and the other with direct laser sintering. Spatially indexed stress-free cubes were obtained by EDM sectioning equivalent prisms of similar shape. The (311) interplanar spacing examined for the EDM sectioned sample was compared to the interplanar spacings calculated to fulfill force and moment balance. We have shown that Applying force and moment balance is a necessary supplement to the measurements for the stress-free cubes with respect to accurate stress calculations in additively manufactured components. Furthermore, our work hasmore » shown that residual stresses in electron beam melting parts are much smaller than that of direct laser metal sintering parts.« less

  6. Extracting spectroscopic factors from direct reactions

    NASA Astrophysics Data System (ADS)

    Jones, Kate

    2009-10-01

    Direct reactions have been used to probe the structure of the nucleus for decades. After some decline in the 80's and 90's these methods have more recently had a surge in popularity, and new techniques have been added to the experimentalists toolbox. One goal of direct reaction experiments is to extract spectroscopic factors (SFs), related to the shell occupancy. SFs extracted from neutron knockout reactions show reductions, compared to the theoretical value, that are related to the neutron separation energy [1], whereas SFs from the well-established (e,e'p) reaction on stable nuclei are consistently 50% - 60% lower than those expected from the independent-particle shell model [2] over a wide range of masses. pardAs the extraction of spectroscopic factors from direct reaction measurements requires the comparison of data with calculated differential cross sections, the results are by nature model dependent. The influence of different scattering (commonly optical), and bound state potentials, should not be over-looked. Recent attempts to reanalyze single-neutron transfer data using a consistent approach have shown agreement with large basis shell model calculations [3], clearly conflicting with both the (e,e'p) and the knockout data. It has been suggested that the Asymptotic Normalization Coefficient (ANC) is a more valid quantity to extract when the reaction is peripheral [4]. spectroscopic factors are, how they are extracted and what they really mean will be discussed in this talk.[4pt] [1] Alexandra Gade, and Thomas Glasmacher, Prog Part. Nucl. Phys. 60 (2008) 161-224.[0pt] [2] G.J. Kramer, H.P. Blok, and L. Lapik'as, Nucl. Phys. A679 (2001) 267-286.[0pt] [3] Jenny Lee, M.B. Tsang, and W.G. Lynch, Phys. Rev C 75, (2007), 064320.[0pt] [4] D.Y. Pan, F.M. Nunes, and A.M. Mukhamedzhanov, Phys. Rev. C 75, (2007) 024601.

  7. Direct Reactions with MoNA-LISA

    NASA Astrophysics Data System (ADS)

    Kuchera, Anthony

    2016-03-01

    Nuclear reactions can be used to probe the structure of nuclei. Direct reactions, which take place on short time scales, are well-suited for experiments with beams of short-lived nuclei. One such reaction is nucleon knockout where a proton or neutron is removed from the incoming beam from the interaction with a target. Single nucleon knockout reactions have been used to study the single-particle nature of nuclear wave functions. A recent experiment at the National Superconducting Cyclotron Laboratory was performed to measure cross sections from single nucleon knockout reactions for several p-shell nuclei. Detection of the residual nucleus in coincidence with any gamma rays emitted from the target allowed cross sections to ground and excited states to be measured. Together with input from reaction theory, ab initio structure theories can be tested. Simultaneously the accuracy of knockout reaction models can be validated by detecting the knocked out neutron with the Modular Neutron Array and Large multi-Institutional Scintillator Array (MoNA-LISA). Preliminary results from this experiment will be shown. Knockout reactions can also be used to populate nuclei which are neutron unbound, thus emit neutrons nearly instantaneously. The structure of these nuclei, therefore, cannot be probed with gamma ray spectroscopy. However, with large neutron detectors like MoNA-LISA the properties of these short-lived nuclei are able to be measured. Recent results using MoNA-LISA to study the structure of neutron-rich nuclei will be presented. The author would like to acknowledge support from the NNSA and NSF.

  8. Excitation of giant resonances via direct reactions

    SciTech Connect

    Bertrand, F.E.

    1982-01-01

    Experimental measurements of electric giant multipole resonances are discussed. The parameters of the giant quadrupole resonance are now firmly established by an extensive set of measurements. The GQR is providing a significant influence in other areas of nuclear physics. The monopole resonance has now been established and its observation has provided the first direct measure of the nuclear compressibility. A strong case for the existence of a giant octupole resonance is now being made through a variety of hadron reactions. However, the supply of giant multipole resonances has not been exhausted. The newer techniques such as higher energy proton scattering, charge exchange reactions, heavy-ion scattering and pion reactions offer considerable hope for identifying new resonances during the next few years.

  9. Direct Reactions studies at RIBF new facility

    NASA Astrophysics Data System (ADS)

    Motobayashi, Tohru

    2009-10-01

    The RIKEN RI Beam Factory (RIBF) is the firs realization of new-generation facilities with beams of unstable nuclei. It is based on heavy-ion primary beams accelerated to 345 MeV/nucleon for all elements up to uranium. When the goal intensity, 1 pμA, is reached, RIBF allows production of about thousand new isotopes with the yield higher than 1 particle par day. Since the RI beam energy after production by in-flight fission and/or projectile fragmentation is be around 200-300 MeV/nucleon, the direct reaction is one of the useful processes for spectroscopy of uncle very far from the stability. Several experiments were proposed and a few of them have been performed with intense (currently) ^48Ca primary beams. The ZeroDegree Spectrometer, which is already operational, can be used to identify the product of a direct reaction in inverse kinematics coupled with, for example, measurement of γ-rays from excited states in the product. Construction of SAMURAI, a large-acceptance spectrometer, has been started. Decays of unbound states or breakup products from various types of direct reaction will be measured in coincidence. Experimental and theoretical issues to be considered for the specific conditions in this new opportunity will be discussed together with brief overview of near-term research.

  10. Sintering in Laser Sintering

    NASA Astrophysics Data System (ADS)

    Bourell, David L.

    2016-03-01

    Laser sintering is a popular additive manufacturing technology, particularly for service parts. Invented by C. Deckard in the mid-1980s, the approach of using a laser to densify a powder bed selectively has been extensively researched and has been applied to metals, ceramics, polymers and composites. In the traditional powder-metallurgical sense, sintering involves solid-state atomic transport resulting in neck formation and eventual densification in a powder mass. The use of the term "sintering" as a descriptive term for the powder-bed additive manufacturing process has been problematical to the technical community, because the predominant densification mechanism has been shown for most applications to be melting and reflow. The term has perpetuated as a name for the additive manufacturing process, at least for polymers. The technical term "sintering" is accurately associated with laser sintering insofar as powder pre-processing and part post-processing are concerned. It may also be used to describe formation of "part cake". This paper describes the circumstances surrounding the coining of the term, "laser sintering" and provides some examples of how sintering is used in pre- and post-processing.

  11. First direct 3D visualisation of microstructural evolutions during sintering through X-ray computed microtomography

    SciTech Connect

    Bernard, Dominique . E-mail: bernard@icmcb.u-bordeaux.fr; Gendron, Damien; Heintz, Jean-Marc; Bordere, Sylvie; Etourneau, Jean

    2005-01-03

    X-ray computed microtomography (XCMT) has been applied to ceramic samples of different materials to visualise, for the first time at this scale, real 3D microstructural evolutions during sintering. Using this technique, it has been possible to follow the whole sintering process of the same grains set. Two materials have been studied; a glass powder heat treated at 700 deg. C and a crystallised lithium borate (Li{sub 6}Gd(BO{sub 3}){sub 3}) powder heat treated at 720 deg. C. XCMT measurements have been done after different sintering times. For each material, a sub-volume was individualised and localised on the successive recordings and its 3D images numerically reconstructed. Description of the three-dimensional microstructures evolution is proposed. From the 3D experimental data, quantitative evolutions of parameters such as porosity and neck size are presented for the glass sample. Possibilities offered by this technique to study complex sintering processes, as for lithium borate, are illustrated.

  12. Fabrication of protective-coated SiC reinforced tungsten matrix composites with reduced reaction phases by spark plasma sintering

    NASA Astrophysics Data System (ADS)

    Umer, Malik Adeel; Lee, Dongju; Waseem, Owais Ahmed; Ryu, Ho Jin; Hong, Soon Hyung

    2016-05-01

    SiC reinforced tungsten matrix composites were fabricated via the spark plasma sintering process. In order to prevent an interfacial reaction between the SiC and tungsten during sintering, TiOx coated SiC particles were synthesized by a solution-based process. TiOx layer coated SiC particles were treated in high temperature nitriding conditions or annealed in a high temperature vacuum to form TiN or TiC coated SiC particles, respectively. The TiC layers coated on SiC particles successfully prevented tungsten from reacting with SiC; hence the proposed process resulted in successful fabrication of the SiC/W composites. The mechanical properties such as compressive strength and flexural strength of the composites were measured. Additionally, the effect of SiC on the high temperature oxidative ablation of tungsten was also investigated. The addition of SiC resulted in an improved oxidative ablation resistance of the tungsten-based composites.

  13. Structural Understanding of Direct-Sintered Al2O3-to-Cu Joints Through Damage Modeling

    NASA Astrophysics Data System (ADS)

    Lis, Adrian; Asama, Koji; Matsuda, Tomoki; Sano

    2017-07-01

    Al2O3-to-Cu/3 μm Ni/1 μm Au assemblies were direct-sintered with a paste consisting of micron-sized Ag2O particles and a reducing solvent that provokes Ag2O-to-Ag reduction during processing accompanied by the formation of Ag nanoparticles. The variation of process temperature, pressure and time resulted in different porosity and shear strength. This experimental data set was used to calibrate a finite element model of the assembly considering the elasto-visco-plastic joint properties and the joint porosity. Local analyses within the sintered Ag layer yielded a damage function D f and a damage criterion that could assess the joint strength as a function of geometry, microstructure and process conditions. The developed damage model introduced a parameter ζ, i.e. the product of equivalent creep strain ɛ cr,eq and stress triaxiality η, that balanced the tolerable equivalent plastic strain ɛ pl,eq at fracture. A Fortran subroutine (UVARM) visualized the damage distribution over the sintered layer. The predominant crack initiation and propagation were identified in good agreement with the experimental fracture behavior. A numerical parameter study subsequently revealed the complex interaction between the ceramic-metal interfacial porosity, the total bulk porosity and the shear strength.

  14. Amyloplast Distribution Directs a Root Gravitropic Reaction

    NASA Astrophysics Data System (ADS)

    Kordyum, Elizabeth

    Immobile higher plants are oriented in the gravitational field due to gravitropim that is a physiological growth reaction and consists of three phases: reception of a gravitational signal by statocytes, its transduction to the elongation zone, and finally the organ bending. As it is known, roots are characterized with positive gravitropism, i. e. they grow in the direction of a gravitational vector, stems - with negative gravitropism, i. e. they grow in the direction opposite to a gravitational vector. According to the Nemec’s and Haberlandt’s starch-statolith hypothesis, amyloplasts in diameter of 1.5 - 3 μ in average, which appear to act as gravity sensors and fulfill a statolythic function in the specialized graviperceptive cells - statocytes, sediment in the direction of a gravitational vector in the distal part of a cell, while a nucleus is in the proximal one. There are reasonable data that confirm the amyloplasts-statoliths participation in gravity perception: 1) correlation between the statoliths localization and the site of gravity sensing, 2) significant redistribution (sedimentation) of amyloplasts in statocytes under gravistimulation in comparison with other cell organelles, 3) root decreased ability to react on gravity under starch removal from amyloplasts, 4) starchless Arabidopsis thaliana mutants are agravitropic, 5) amyloplasts-statoliths do not sediment in the absence of the gravitational vector and are in different parts or more concentrated in the center of statocytes. Plant tropisms have been intensively studied for many decades and continue to be investigated. Nevertheless, the mechanisms by which plants do so is still not clearly explained and many questions on gravisensing and graviresponse remain unanswered. Even accepted hypotheses are now being questioned and recent data are critically evaluated. Although the available data show the Ca2+ and cytoskeleton participation in graviperception and signal transduction, the clear evidence

  15. Development of Continuous, Direct Feedback Control Systems for Sintering of Metallic Components

    SciTech Connect

    Diran Apelian; Marc M. Baum

    2006-09-18

    N,N.-Ethylenebisstearimide (EBS) is one of the most commonlyused lubricants in the powder metallurgy (PM) industry in the sintering process. During sintering, the lubricated powder compacts are heat-treated to temperatures in excess of 1,200 °C thus fusing adjacent particles and yielding a part with improved mechanical strength. Delubrication commonly is achieved in the first zone of a sintering furnace by heating the part to temperatures in the 500-600 °C temperature range at a fixed rate and under controlled atmospheric conditions; this strategy minimizes defects, carbon contamination, and compact deformation. The de-lubricated part then enters the second zone (commonly in the 1200-1300 °C temperature range) for sintering. The third zone cools the sintered part at a desired rate to obtain the requisite micro-structural properties. Controlled delubrication is imperative towards achieving high quality parts for the following reasons: the elevated thermal gradient at the transition between the first and second zones can cause parts to expand rapidly and develop microscopic fissures (.blistering.); improper gas flows and belt speeds can lead to carbon deposition on the part and at the grain boundaries (sooting); delubrication products deposit throughout the furnace, even in the coolers, which are far removed from the preheating chamber, leading to significant maintenance costs; pollutants emitted in the exhaust stream of furnaces operating inefficiently are increasingly of environmental concern. In practice, lubricant removal is difficult to control, which often leads to reduced yields in PM manufacturing processes. Throughput is another important issue: process control ideally should lead to a delubrication cycle that yields defect-free parts in a minimum of furnace time, thereby increasing productivity and reducing the net energy consumption. Efficient process control requires rapid monitoring of suitable indicators, preferably gasphase products of delubrication

  16. Apparatus for direct measurement of ash fusion and sintering behavior at elevated temperatures and pressures

    NASA Astrophysics Data System (ADS)

    Khan, M. Rashid

    1989-10-01

    Ash fusion, sintering, and deposition may impose serious operational difficulties in conventional and advanced coal-combustion systems. Conventional ash fusion techniques (e.g., ASTM methods) determine the qualitative behavior of ash samples at atmospheric pressure. Presently, there is no known available technique that can measure the behavior of coal ash at elevated temperatures and pressures. In the literature, methods based on electrical resistance or shrinkage of coal ash have been reported at atmospheric pressure (elevated temperatures) conditions. A high-pressure microdilatometer (HPMD) has been developed to investigate ash fusion and sintering behavior at elevated pressures and temperatures by the simultaneous measurement of the temperature of initial contraction and electrical resistivity of samples. This novel technique facilitates the measurement of ash properties over a wide range of temperature, pressure, and gas atmosphere (oxidizing, reducing, or inert). The operating principle of the HPMD includes measuring the temperature at which there is a significant ``shift'' in the electrical resistivity (and/or sample volume) that represents ash sintering and fusion. Sintering occurs through the formation of solid-state, particle-to-particle ``necks'' or the appearance of a molten phase, which allows a path for electrical conductance. The ability to perform both resistivity and shrinkage measurements simultaneously or independently at elevated pressures makes the HPMD truly unique. The HPMD can also be used to investigate the swelling and softening behavior of pyrolyzing coal at elevated pressures and relatively rapid heating rates. The HPMD can provide insights into the sintering/fusion of coal ash or coal swelling at a range of conditions: (a) the influences of various gas atmospheres can be investigated, (b) the effects of pressure can be studied, (c) different temperature/heating rate schemes can be used (constant rates, isothermal holds below or above the

  17. Silver conductive features on flexible substrates from a thermally accelerated chain reaction at low sintering temperatures.

    PubMed

    Chen, Shih-Pin; Kao, Zhen-Kai; Lin, Jeng-Lung; Liao, Ying-Chih

    2012-12-01

    In this study, a simple and effective silver ink formulation was developed to generate silver tracks with high electrical conductivity on flexible substrates at low sintering temperatures. Diethanolamine (DEA), a self-oxidizing compound at moderate temperatures, was mixed with a silver ammonia solution to form a clear and stable solution. After inkjet-printed or pen-written on plastic sheets, DEA in the silver ink decomposes at temperatures higher than 50 °C and generates formaldehyde, which reacts spontaneously with silver ammonia ions to form silver thin films. The electrical conductivity of the inkjet-printed silver films can be 26% of the bulk silver after heating at 75 °C for 20 min and show great adhesion on plastic sheets.

  18. Sintering of the reaction products of combustion of alloys in nitrogen

    SciTech Connect

    Maksimov, Y.M.; Raskolenko, L.G.; Zepakova, O.K.; Ziatdinov, M.K.

    1986-05-01

    An investigation of the mechanism of compacting of Fe-V alloy with a sigma-phase structure, a low porosity composite material consisting of alpha-iron and a filler of delta-vanadium nitride, is made after the synthesis surge. Alloys containing 50 wt.% Fe were prepared by sintering in a vacuum furnace of powders of type VEL-1 vandium and special purity carbonyl iron. The mechanism of compacting was studied on specimens in hardened water. Metallographic investigations were made on MIM-7 and PMT-3 instruments and the phase analysis on a DRON-2 instrument. Rapid compacting in combustion of sigma-FeV in nitrogen is determined by combining of the solid-liquid drops formed in the combustion front and consisting of molten iron and vanadium nitrides.

  19. Ultrasmooth reaction-sintered silicon carbide surface resulting from combination of thermal oxidation and ceria slurry polishing.

    PubMed

    Shen, Xinmin; Dai, Yifan; Deng, Hui; Guan, Chaoliang; Yamamura, Kazuya

    2013-06-17

    An ultrasmooth reaction-sintered silicon carbide surface with an rms roughness of 0.424 nm is obtained after thermal oxidation for 30 min followed by ceria slurry polishing for 30 min. By SEM-EDX analysis, we investigated the thermal oxidation behavior of RS-SiC, in which the main components are Si and SiC. As the oxidation rate is higher in the area with defects, there are no scratches or cracks on the surface after oxidation. However, a bumpy structure is formed after oxidation because the oxidation rates of Si and SiC differ. Through a theoretical analysis of thermal oxidation using the Deal-Grove model and the removal of the oxide layer by ceria slurry polishing in accordance with the Preston equation, a model for obtaining an ultrasmooth surface is proposed and the optimal processing conditions are presented.

  20. Effect of Z Values on the Microstructure and Mechanical Properties of Post-sintered Reaction Bonded β-SiAlON

    NASA Astrophysics Data System (ADS)

    Li, Yanjun; Liu, Donghua; Jin, Han; Ding, Donghai; Xiao, Guoqing; Shi, Zhongqi; Jin, Zhihao

    2017-05-01

    β-SiAlON materials with different Z values (Z=0.5-3) were fabricated by a reaction bonding combining post-sintering route using raw materials of Si, Al2O3, AlN, etc. The reaction bonded β-SiAlON (RB-β-SiAlON) were post-sintered at 1,750 °C for 6 h. Apparent porosity, bulk density, bending strength and Vicker's hardness of the samples before and after post-sintering were tested. XRD results showed that the phase composition of both RB-β-SiAlON and post-sintered RB-β-SiAlON (PSRB-β-SiAlON) were β-SiAlON. For RB-β-SiAlON, the apparent porosity was decreased with the increase of Z values, while the strength and hardness was increased accordingly. After the post-sintering procedure, nearly full densified PSRB-β-SiAlON was obtained and the mechanical properties were significantly improved. The bending strength and Vicker's hardness of the PSRB-β-SiAlON (Z=0.5) achieved 510 MPa and 16.5 GPa, respectively, which were as 2.7 and 6.7 times high as those of the corresponding RB-β-SiAlON. However, the strength and hardness of PSRB-β-SiAlON decreased with the increase of Z value due to the grain growth.

  1. Apparatus and method for direct measurement of coal ash sintering and fusion properties at elevated temperatures and pressures

    DOEpatents

    Khan, M. Rashid

    1990-01-01

    A high-pressure microdilatometer is provided for measuring the sintering and fusion properties of various coal ashes under the influence of elevated pressures and temperatures in various atmospheres. Electrical resistivity measurements across a sample of coal ash provide a measurement of the onset of the sintering and fusion of the ash particulates while the contraction of the sample during sintering is measured with a linear variable displacement transducer for detecting the initiation of sintering. These measurements of sintering in coal ash at different pressures provide a mechanism by which deleterious problems due to the sintering and fusion of ash in various combustion systems can be minimized or obviated.

  2. Direct metal laser sintering (DMLS) of a customized titanium mesh for prosthetically guided bone regeneration of atrophic maxillary arches.

    PubMed

    Ciocca, L; Fantini, M; De Crescenzio, F; Corinaldesi, G; Scotti, R

    2011-11-01

    This study describes a protocol for the direct manufacturing of a customized titanium mesh using CAD-CAM procedures and rapid prototyping to augment maxillary bone and minimize surgery when severe atrophy or post-oncological deformities are present. Titanium mesh and particulate autogenous plus bovine demineralised bone were planned for patient rehabilitation. Bone augmentation planning was performed using the pre-op CT data set in relation to the prosthetic demands, minimizing the bone volume to augment at the minimum necessary for implants. The containment mesh design was used to prototype the 0.6 mm thickness customized titanium mesh, by direct metal laser sintering. The levels of regenerated bone were calculated using the post-op CT data set, through comparison with the pre-op CT data set. The mean vertical height difference of the crestal bone was 2.57 mm, while the mean buccal-palatal dimension of thickness difference was 3.41 mm. All planned implants were positioned after an 8 month healing period using two-step implant surgery, and finally restored with a partial fixed prosthesis. We present a viable and reproducible method to determine the correct bone augmentation prior to implant placement and CAD-CAM to produce a customized direct laser-sintered titanium mesh that can be used for bone regeneration.

  3. Structure and properties of porous TiNi(Co, Mo)-based alloy produced by the reaction sintering

    NASA Astrophysics Data System (ADS)

    Artyukhova, Nadezda; Yasenchuk, Yuriy; Chekalkin, Timofey; Gunther, Victor; Kim, Ji-Soon; Kang, Ji-Hoon

    2016-10-01

    Modern medical technologies have developed many new devices that can be implanted into humans to repair, assist or take the place of diseased or defective bones, arteries and even organs. The materials, especially porous ones, used for these devices have evolved steadily over the past twenty years with TiNi-based alloys replacing stainless steels and titanium. The aim of the paper is to presents results for examination of porous TiNi(Co,Mo)-based alloys intended further to be used in clinical practice. The structure and properties of porous TiNi-based alloys obtained by reaction sintering of Ti and Ni powders with additions of Co and Mo have been studied. It has been shown that alloying additions both Co and Mo inhibit the compaction of nickel powders in the initial stage of sintering. The maximum irreversible strain of porous samples under loading in the austenitic state is fixed with the Co addition, and the minimum one is fixed with the Mo addition. The Co addition leads to the fact that the martensite transformation in the TiNi phase becomes close to a one-step, and the Mo addition leads to the fact that the martensite transformation becomes more uniform. Both Co and Mo lead to an increase in the maximum accumulated strain as a result of the formation of temperature martensite. The additional increase in the maximum accumulated strain of the Ti50Ni49Co1 alloy is caused by decreased resistance of the porous Ni γ -based mass during the load.

  4. The role of La2O3 in direct laser sintering of submicrometre WC Cop/Cu MMCs

    NASA Astrophysics Data System (ADS)

    Gu, Dongdong; Shen, Yifu

    2008-05-01

    This paper presents a detailed investigation of the influence of rare earth (RE) oxide (La2O3) addition on densification and microstructure of direct laser sintered submicrometre WC-Cop/Cu metal matrix composites (MMCs) possessing 50.0 wt% reinforcement (WC-Co). It was found that with increasing La2O3 addition to a suitable amount (1.0 wt%), the particulate dispersion was homogenized and the particulate/matrix interfacial bonding was improved. However, with an excessive addition of La2O3 (1.5 wt%), a heterogeneous microstructure consisting of highly accumulated particulates was present. The exact metallurgical roles of RE element in direct laser sintering of particulate reinforced MMCs were addressed. It showed that a proper addition of RE element (i) decreased surface tension of the melt and enhanced solid-liquid wettability; (ii) dragged and/or pinned grain/phase boundaries and resisted grain coarsening and particulate aggregating. However, the balling phenomenon occurred and the activity of RE atoms decreased at an even higher La2O3 content, thereby producing detrimental effects on laser forming ability.

  5. Establishing Antibacterial Multilayer Films on the Surface of Direct Metal Laser Sintered Titanium Primed with Phase-Transited Lysozyme.

    PubMed

    Guan, Binbin; Wang, Haorong; Xu, Ruiqing; Zheng, Guoying; Yang, Jie; Liu, Zihao; Cao, Man; Wu, Mingyao; Song, Jinhua; Li, Neng; Li, Ting; Cai, Qing; Yang, Xiaoping; Li, Yanqiu; Zhang, Xu

    2016-11-08

    Direct metal laser sintering is a technology that allows the fabrication of titanium (Ti) implants with a functional gradation of porosity and surface roughness according to three-dimensional (3D) computer data. The surface roughness of direct metal laser sintered titanium (DMLS-Ti) implants may provide abundant binding sites for bacteria. Bacterial colonization and subsequent biofilm formation can cause unsatisfactory cell adhesion and implant-related infections. To prevent such infections, a novel phase-transited lysozyme (PTL) was utilized as an initial functional layer to simply and effectively prime DMLS-Ti surfaces for subsequent coating with antibacterial multilayers. The purpose of the present study was to establish a surface with dual biological functionality. The minocycline-loaded polyelectrolyte multilayers of hyaluronic acid (HA) and chitosan (CS) formed via a layer-by-layer (LbL) self-assembly technique on PTL-functionalized DMLS-Ti were designed to inhibit pathogenic microbial infections while allowing the DMLS-Ti itself and the modified coatings to retain acceptable biocompatibility. The experimental results indicate that the DMLS-Ti and the hydrogel treated surfaces can inhibit early bacterial adhesion while completely preserving osteoblast functions. This design is expected to gain considerable interest in the medical field and to have good potential for applications in multifunctional DMLS-Ti implants.

  6. Establishing Antibacterial Multilayer Films on the Surface of Direct Metal Laser Sintered Titanium Primed with Phase-Transited Lysozyme

    NASA Astrophysics Data System (ADS)

    Guan, Binbin; Wang, Haorong; Xu, Ruiqing; Zheng, Guoying; Yang, Jie; Liu, Zihao; Cao, Man; Wu, Mingyao; Song, Jinhua; Li, Neng; Li, Ting; Cai, Qing; Yang, Xiaoping; Li, Yanqiu; Zhang, Xu

    2016-11-01

    Direct metal laser sintering is a technology that allows the fabrication of titanium (Ti) implants with a functional gradation of porosity and surface roughness according to three-dimensional (3D) computer data. The surface roughness of direct metal laser sintered titanium (DMLS-Ti) implants may provide abundant binding sites for bacteria. Bacterial colonization and subsequent biofilm formation can cause unsatisfactory cell adhesion and implant-related infections. To prevent such infections, a novel phase-transited lysozyme (PTL) was utilized as an initial functional layer to simply and effectively prime DMLS-Ti surfaces for subsequent coating with antibacterial multilayers. The purpose of the present study was to establish a surface with dual biological functionality. The minocycline-loaded polyelectrolyte multilayers of hyaluronic acid (HA) and chitosan (CS) formed via a layer-by-layer (LbL) self-assembly technique on PTL-functionalized DMLS-Ti were designed to inhibit pathogenic microbial infections while allowing the DMLS-Ti itself and the modified coatings to retain acceptable biocompatibility. The experimental results indicate that the DMLS-Ti and the hydrogel treated surfaces can inhibit early bacterial adhesion while completely preserving osteoblast functions. This design is expected to gain considerable interest in the medical field and to have good potential for applications in multifunctional DMLS-Ti implants.

  7. Establishing Antibacterial Multilayer Films on the Surface of Direct Metal Laser Sintered Titanium Primed with Phase-Transited Lysozyme

    PubMed Central

    Guan, Binbin; Wang, Haorong; Xu, Ruiqing; Zheng, Guoying; Yang, Jie; Liu, Zihao; Cao, Man; Wu, Mingyao; Song, Jinhua; Li, Neng; Li, Ting; Cai, Qing; Yang, Xiaoping; Li, Yanqiu; Zhang, Xu

    2016-01-01

    Direct metal laser sintering is a technology that allows the fabrication of titanium (Ti) implants with a functional gradation of porosity and surface roughness according to three-dimensional (3D) computer data. The surface roughness of direct metal laser sintered titanium (DMLS-Ti) implants may provide abundant binding sites for bacteria. Bacterial colonization and subsequent biofilm formation can cause unsatisfactory cell adhesion and implant-related infections. To prevent such infections, a novel phase-transited lysozyme (PTL) was utilized as an initial functional layer to simply and effectively prime DMLS-Ti surfaces for subsequent coating with antibacterial multilayers. The purpose of the present study was to establish a surface with dual biological functionality. The minocycline-loaded polyelectrolyte multilayers of hyaluronic acid (HA) and chitosan (CS) formed via a layer-by-layer (LbL) self-assembly technique on PTL-functionalized DMLS-Ti were designed to inhibit pathogenic microbial infections while allowing the DMLS-Ti itself and the modified coatings to retain acceptable biocompatibility. The experimental results indicate that the DMLS-Ti and the hydrogel treated surfaces can inhibit early bacterial adhesion while completely preserving osteoblast functions. This design is expected to gain considerable interest in the medical field and to have good potential for applications in multifunctional DMLS-Ti implants. PMID:27821857

  8. Preliminary study on atmospheric-pressure plasma-based chemical dry figuring and finishing of reaction-sintered silicon carbide

    NASA Astrophysics Data System (ADS)

    Shen, Xinmin; Deng, Hui; Zhang, Xiaonan; Peng, Kang; Yamamura, Kazuya

    2016-10-01

    Reaction-sintered silicon carbide (RS-SiC) is a research focus in the field of optical manufacturing. Atmospheric-pressure plasma-based chemical dry figuring and finishing, which consist of plasma chemical vaporization machining (PCVM) and plasma-assisted polishing (PAP), were applied to improve material removal rate (MRR) in rapid figuring and ameliorate surface quality in fine finishing. Through observing the processed RS-SiC sample in PCVM by scanning white-light interferometer (SWLI), the calculated peak-MRR and volume-MRR were 0.533 μm/min and 2.78×10-3 mm3/min, respectively. The comparisons of surface roughness and morphology of the RS-SiC samples before and after PCVM were obtained by the scanning electron microscope and atomic force microscope. It could be found that the processed RS-SiC surface was deteriorated with surface roughness rms 382.116 nm. The evaluations of surface quality of the processed RS-SiC sample in PAP corresponding to different collocations of autorotation speed and revolution speed were obtained by SWLI measurement. The optimal surface roughness rms of the processed RS-SiC sample in PAP was 2.186 nm. There were no subsurface damages, scratches, or residual stresses on the processed sample in PAP. The results indicate that parameters in PAP should be strictly selected, and the optimal parameters can simultaneously obtain high MRR and smooth surface.

  9. Investigation on the formation of projections and cracks in anodic oxidation of reaction-sintered silicon carbide

    NASA Astrophysics Data System (ADS)

    Peng, Kang; Shen, Xinmin; Yamamura, Kazuya; Zhang, Xiaonan; Wang, Dong

    2017-01-01

    Among the present oxidation-assisted polishing (OAP) technique, anodic oxidation is a promising method to process reaction-sintered silicon carbide (RS-SiC) with the assistance of abrasive polishing. Projections and cracks are inevitably formed in the anodic oxidation of RS-SiC for the volume expansion force. Evolvements of the oxide morphologies along with different oxidation voltage and different oxidation time are investigated by scanning electron microscope (SEM). It can be found that when the oxidation time stays the same, size of the projections and cracks on the oxidized RS-SiC sample is gradually enlarged. Meanwhile, when the oxidation voltage stays the same, size of the projections and cracks on the oxidized RS-SiC sample is also enlarged. Details of projections and cracks on the oxidized RS-SiC sample are obtained by the SEM with high magnification. Based on the theoretical derivation, it can be concluded that the formations of projections and cracks depend on the inner volume expansion force and the resultant force generated from other grains. Research on formation of projections and cracks in anodic oxidation of RS-SiC can promote the process level of RS-SiC products.

  10. Effects of Sm2O3 Content on the Microstructure and Mechanical Properties of Post-Sintered Reaction-Bonded β-SiAlON

    NASA Astrophysics Data System (ADS)

    Li, Yanjun; Liu, Donghua; Zeng, Cunfeng; Shi, Zhongqi; Jin, Zhihao

    2016-03-01

    β-SiAlON materials were fabricated by a reaction bonding combining post-sintering route using raw materials of Si, Al2O3, AlN, etc. Sm2O3 was used as sintering additive with the content of 0, 2, 4, and 6 wt.%, respectively. The reaction-bonded β-SiAlON (RB-β-SiAlON) were post sintered at 1750 °C for 6 h. XRD results showed that the phase composition of both RB-β-SiAlON and post-sintered RB-β-SiAlON (PSRB-β-SiAlON) was β-SiAlON. For RB-β-SiAlON, the apparent porosity was decreased with the increase of Sm2O3 content, while the bending strength (σf) and Vicker's hardness (HV10) was increased accordingly. After the post-sintering procedure, nearly full densified PSRB-β-SiAlON was obtained and the mechanical properties were significantly improved with the addition of Sm2O3 additive. The σf and HV10 of the PSRB-β-SiAlON (4 wt.% Sm2O3) achieved 520 MPa and 16.4 GPa, respectively, which were as 3.5 and 6.3 times high as those of the corresponding RB-β-SiAlON. The Young's modulus (E) and the fracture toughness (K IC) of the dense PSRB-β-SiAlON were increased with the increase of the Sm2O3 content.

  11. Development of energy-absorbing reaction-sintered Si3N4 surface layers on hot-pressed Si3N4

    NASA Technical Reports Server (NTRS)

    Brennan, J. J.

    1981-01-01

    Energy-absorbing Si3N4 surface layers on dense Si3N4 substrates were formed by in-place nitridation of fine-grained silicon powder. Ballistic impact tests performed on samples with 1-mm thick layers at room temperature and 1370 C showed up to an eightfold increase in the energy necessary to fracture the substrate. For maximum impact resistance, a small amount (about 20 vol %) of residual Si must be present in the reaction-sintered Si3N4 surface layer. Thermal cycling to 1370 C did not affect impact resistance, even though a considerable amount of SiO2 formed within the reaction-sintered Si3N4 layer during cycling. Erosion testing of samples in a Mach 0.8 burner rig at 1370 C resulted in minimal surface recession of the surface layer. Chemically vapor-deposited SiC-coated material similarly tested exhibited no surface recession.

  12. Development of energy-absorbing reaction-sintered Si3N4 surface layers on hot-pressed Si3N4

    NASA Technical Reports Server (NTRS)

    Brennan, J. J.

    1981-01-01

    Energy-absorbing Si3N4 surface layers on dense Si3N4 substrates were formed by in-place nitridation of fine-grained silicon powder. Ballistic impact tests performed on samples with 1-mm thick layers at room temperature and 1370 C showed up to an eightfold increase in the energy necessary to fracture the substrate. For maximum impact resistance, a small amount (about 20 vol %) of residual Si must be present in the reaction-sintered Si3N4 surface layer. Thermal cycling to 1370 C did not affect impact resistance, even though a considerable amount of SiO2 formed within the reaction-sintered Si3N4 layer during cycling. Erosion testing of samples in a Mach 0.8 burner rig at 1370 C resulted in minimal surface recession of the surface layer. Chemically vapor-deposited SiC-coated material similarly tested exhibited no surface recession.

  13. Experimental analysis on semi-finishing machining of Ti6Al4V additively manufactured by direct melting laser sintering

    NASA Astrophysics Data System (ADS)

    Imbrogno, Stano; Bordin, Alberto; Bruschi, Stefania; Umbrello, Domenico

    2016-10-01

    The Additive Manufacturing (AM) techniques are particularly appealing especially for titanium aerospace and biomedical components because they permit to achieve a strong reduction of the buy-to-fly ratio. However, finishing machining operations are often necessary to reduce the uneven surface roughness and geometrics because of local missing accuracy. This work shows the influence of the cutting parameters, cutting speed and feed rate, on the cutting forces as well as on the thermal field observed in the cutting zone, during a turning operation carried out on bars made of Ti6Al4V obtained by the AM process called Direct Metal Laser Sintering (DMLS). Moreover, the sub-surface microstructure alterations due to the process are also showed and commented.

  14. Tensile Properties Characterization of AlSi10Mg Parts Produced by Direct Metal Laser Sintering via Nested Effects Modeling.

    PubMed

    Palumbo, Biagio; Del Re, Francesco; Martorelli, Massimo; Lanzotti, Antonio; Corrado, Pasquale

    2017-02-08

    A statistical approach for the characterization of Additive Manufacturing (AM) processes is presented in this paper. Design of Experiments (DOE) and ANalysis of VAriance (ANOVA), both based on Nested Effects Modeling (NEM) technique, are adopted to assess the effect of different laser exposure strategies on physical and mechanical properties of AlSi10Mg parts produced by Direct Metal Laser Sintering (DMLS). Due to the wide industrial interest in AM technologies in many different fields, it is extremely important to ensure high parts performances and productivity. For this aim, the present paper focuses on the evaluation of tensile properties of specimens built with different laser exposure strategies. Two optimal laser parameters settings, in terms of both process quality (part performances) and productivity (part build rate), are identified.

  15. Integration of Heat Treatment with Shot Peening of 17-4 Stainless Steel Fabricated by Direct Metal Laser Sintering

    NASA Astrophysics Data System (ADS)

    AlMangour, Bandar; Yang, Jenn-Ming

    2017-08-01

    Direct metal laser sintering (DMLS) is a promising powder-based additive manufacturing process for fabrication of near-net-shape parts. However, the typically poor fatigue performance of DMLS parts must be addressed for use in demanding industrial applications. Post-treatment can be applied to enhance the performance of such components. Earlier attempts at inducing grain refinement through severe plastic deformation of part surfaces using shot peening improved the physical and mechanical properties of metals without chemical alteration. However, heat treatment can modify the surface-hardening effects attained by shot peening. Hence, we examined the feasibility of applying shot peening combined with heat treatment to improve the performance of DMLS-fabricated 17-4 stainless steel parts through microstructural evolution studies and hardness measurements. Compared to a specimen treated only by shot peening, the sample exposed to additional heat treatment showed increased hardness due to aging of the dominant phase.

  16. Tensile Properties Characterization of AlSi10Mg Parts Produced by Direct Metal Laser Sintering via Nested Effects Modeling

    PubMed Central

    Palumbo, Biagio; Del Re, Francesco; Martorelli, Massimo; Lanzotti, Antonio; Corrado, Pasquale

    2017-01-01

    A statistical approach for the characterization of Additive Manufacturing (AM) processes is presented in this paper. Design of Experiments (DOE) and ANalysis of VAriance (ANOVA), both based on Nested Effects Modeling (NEM) technique, are adopted to assess the effect of different laser exposure strategies on physical and mechanical properties of AlSi10Mg parts produced by Direct Metal Laser Sintering (DMLS). Due to the wide industrial interest in AM technologies in many different fields, it is extremely important to ensure high parts performances and productivity. For this aim, the present paper focuses on the evaluation of tensile properties of specimens built with different laser exposure strategies. Two optimal laser parameters settings, in terms of both process quality (part performances) and productivity (part build rate), are identified. PMID:28772505

  17. A newly-developed effective direct current assisted sintering technique for electrolyte film densification of anode-supported solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Liu, Yajie; Hao, Xiaoming; Wang, Zhenhua; Wang, Jiawei; Qiao, Jinshuo; Yan, Yiming; Sun, Kening

    2012-10-01

    In order to lower the sintering temperature and shorten firing time, a novel, effective and facile technique has been developed for sintering Yttria-stabilized zirconia (YSZ) electrolyte thin film. Herein this technique, which employs a weak direct current (DC), is used for the first time in the manufacture of the anode-supported solid oxide fuel cell (SOFC). A single cell is directly assembled using a pre-sintered anode/electrolyte and screen printed cathode and subsequently sintered under electric assistance from room temperature to 800 °C at a heating rate of 5 °C min-1. A fully dense YSZ electrolyte film can be observed by scanning electron microscopy (SEM) and the open circuit voltages (OCVs) are in accordance with theoretical values, confirming that the cell possesses a dense YSZ film. Using hydrogen fuel, the maximum power density of this cell was 0.8, 1.1 and 1.4 W cm-2 at 650, 700 and 750 °C, respectively. We believe this DC assisted sintering technique (DC-AST) may not only reduce the cost, but also maintain the anode nanostructure, thus offering a potentially useful manufacturing technique for SOFCs.

  18. Research on optimal process parameters in thermally oxidation-assisted polishing of reaction-sintered silicon carbide

    NASA Astrophysics Data System (ADS)

    Shen, Xinmin; Yamamura, Kazuya; Zhang, Xiaonan; Zhang, Xiangpo; Wang, Dong; Peng, Kang

    2016-10-01

    Reaction-sintered silicon carbide (RS-SiC) has been widely used in space telescope systems for its excellent physical and mechanical properties. Thermally oxidation-assisted polishing is a practical machining method to obtain RS-SiC parts with high precision, and the research focus is optimization of process parameters, because there are bumpy structures on the oxidized RS-SiC. By atomic force microscopy (AFM) detection, the distributions of oxides on the oxidized RS-SiC sample are quantitative analyzed when the thermal oxidation time is 5min, 30min, and 60min, and the calculated average differences of oxide heights between the initial Si grains and SiC grains are 10.7nm, 25.1nm, and 35.2nm, respectively. Meanwhile, the volume expansion coefficient in oxidation of Si/SiC to SiO2 is 2.257 and 2.194, respectively. Through theoretical derivation based on the Deal-Grove model, the numerical relationship between differences of oxide heights and thermal oxidation time is obtained. Combining with the material removal rate of oxide by ceria slurry in the abrasive polishing, the obtained surface quality can be precisely forecasted and controlled. The oxidized RS-SiC sample, when the oxidation time is 30min, is polished with different times to verify the theoretical analysis results. When the polishing times are 20min, 30min, and 40min, the obtained differences of oxide heights by the AFM detection are consistent with theoretical calculated results. Research on the optimal process parameters in thermally oxidation-assisted polishing of RS-SiC can improve the process level of RS-SiC sample and promote the application of SiC parts.

  19. Ti-O Direct-Current-Sintered Bodies and Their Use for Sputter Deposition of TiO Thin Films: Fabrication and Characterization

    NASA Astrophysics Data System (ADS)

    Tomozawa, Masanari; Ozaki, Kimihiro; Mikami, Masashi; Kobayashi, Keizo

    2010-08-01

    Ti-50at.%O and Ti-40at.%O sintered bodies were fabricated by direct-current sintering using Ti and TiO2 powders as starting materials. Their microstructures were investigated by x-ray diffraction and optical microscopy. Ti-O thin films were deposited on glass substrates by radiofrequency (RF) magnetron sputtering using a Ti-50at.%O or Ti-40at.%O sintered body as a sputtering target. A crystalline TiO thin film was obtained using a Ti-40at.%O sputtering target, while an amorphous or Ti6O11 thin film was obtained using a Ti-50at.%O sputtering target. The electric resistivity of the TiO thin films was 450 μΩ cm to 1000 μΩ cm depending on their thickness.

  20. Direct nuclear reaction experiments for stellar nucleosynthesis

    NASA Astrophysics Data System (ADS)

    Cherubini, S.

    2017-09-01

    During the last two decades indirect methods where proposed and used in many experiments in order to measure nuclear cross sections between charged particles at stellar energies. These are among the lowest to be measured in nuclear physics. One of these methods, the Trojan Horse method, is based on the Quasi-Free reaction mechanism and has proved to be particularly flexible and reliable. It allowed for the measurement of the cross sections of various reactions of astrophysical interest using stable beams. The use and reliability of indirect methods become even more important when reactions induced by Radioactive Ion Beams are considered, given the much lower intensity generally available for these beams. The first Trojan Horse measurement of a process involving the use of a Radioactive Ion Beam dealt with the ^{18} F(p, α ^{15} O process in Nova conditions. To obtain pieces of information on this process, in particular about its cross section at Nova energies, the Trojan Horse method was applied to the ^{18} F(d, α ^{15} O)n three body reaction. In order to establish the reliability of the Trojan Horse method approach, the Treiman-Yang criterion is an important test and it will be addressed briefly in this paper.

  1. Chemical reactions directed Peptide self-assembly.

    PubMed

    Rasale, Dnyaneshwar B; Das, Apurba K

    2015-05-13

    Fabrication of self-assembled nanostructures is one of the important aspects in nanoscience and nanotechnology. The study of self-assembled soft materials remains an area of interest due to their potential applications in biomedicine. The versatile properties of soft materials can be tuned using a bottom up approach of small molecules. Peptide based self-assembly has significant impact in biology because of its unique features such as biocompatibility, straight peptide chain and the presence of different side chain functionality. These unique features explore peptides in various self-assembly process. In this review, we briefly introduce chemical reaction-mediated peptide self-assembly. Herein, we have emphasised enzymes, native chemical ligation and photochemical reactions in the exploration of peptide self-assembly.

  2. Chemical Reactions Directed Peptide Self-Assembly

    PubMed Central

    Rasale, Dnyaneshwar B.; Das, Apurba K.

    2015-01-01

    Fabrication of self-assembled nanostructures is one of the important aspects in nanoscience and nanotechnology. The study of self-assembled soft materials remains an area of interest due to their potential applications in biomedicine. The versatile properties of soft materials can be tuned using a bottom up approach of small molecules. Peptide based self-assembly has significant impact in biology because of its unique features such as biocompatibility, straight peptide chain and the presence of different side chain functionality. These unique features explore peptides in various self-assembly process. In this review, we briefly introduce chemical reaction-mediated peptide self-assembly. Herein, we have emphasised enzymes, native chemical ligation and photochemical reactions in the exploration of peptide self-assembly. PMID:25984603

  3. Sequential reactions directed by core/shell catalytic reactors.

    PubMed

    Wei, Yanhu; Soh, Siowling; Apodaca, Mario M; Kim, Jiwon; Grzybowski, Bartosz A

    2010-04-09

    Millimeter-sized reactor particles made of permeable polymer doped with catalysts arranged in a core/shell fashion direct sequences of chemical reactions (e.g., alkyne coupling followed by hydrogenation or hydrosilylation followed by hydrogenation). Spatial compartmentalization of catalysts coupled with the diffusion of substrates controls reaction order and avoids formation of byproducts. The experimentally observed yields of reaction sequences are reproduced by a theoretical model, which accounts for the reaction kinetics and the diffusion of the species involved.

  4. Toward Direct Reaction-in-Flight Measurements

    NASA Astrophysics Data System (ADS)

    Wilhelmy, Jerry; Bredeweg, Todd; Fowler, Malcolm; Gooden, Matthew; Hayes, Anna; Rusev, Gencho; Caggiano, Joseph; Hatarik, Robert; Henry, Eugene; Tonchev, Anton; Yeaman, Charles; Bhike, Megha; Krishichayan, Krishi; Tornow, Werner

    2016-03-01

    At the National Ignition Facility (NIF) neutrons having energies greater than the equilibrium 14.1 MeV value can be produced via Reaction-in-Flight (RIF) interactions between plasma atoms and upscattered D or T ions. The yield and spectrum of these RIF produced neutrons carry information on the plasma properties as well as information on the stopping power of ions under plasma conditions. At NIF the yield of these RIF neutrons is predicted to be 4-7 orders of magnitude below the peak 14 MeV neutron yield. The current generation of neutron time of flight (nTOF) instrumentation has so far been incapable of detecting these low-yield neutrons primarily due to high photon backgrounds. To date, information on RIF neutrons has been obtained in integral activation experiments using reactions with high energy thresholds such as 169Tm(n,3n)167Tm and 209Bi(n,4n) 206Bi. Initial experiments to selectively suppress photon backgrounds have been performed at TUNL using pulsed monoenergetic neutron beams of 14.9, 18.5, 24.2, and 28.5 MeV impinging on a Bibenzyl scintillator. By placing 5 cm of Pb before the scintillator we were able to selectively suppress the photons from the flash occurring at the production target and enhance the n/_signal by ~6 times.

  5. Direct Reactions for Nuclear Structure and Nuclear Astrophysics

    SciTech Connect

    Jones, Katherine Louise

    2014-12-18

    Direct reactions are powerful probes for studying the atomic nucleus. Modern direct reaction studies are illuminating both the fundamental nature of the nucleus and its role in nucleosynthetic processes occurring in the cosmos. This report covers experiments using knockout reactions on neutron-deficient fragmentation beams, transfer reactions on fission fragment beams, and theoretical sensitivity studies relating to the astrophysical r-process. Results from experiments on 108,106Sn at the NSCL, and on 131Sn at HRIBF are presented as well as the results from the nucleosynthesis study.

  6. Maxillary overdentures supported by four splinted direct metal laser sintering implants: a 3-year prospective clinical study.

    PubMed

    Mangano, Francesco; Luongo, Fabrizia; Shibli, Jamil Awad; Anil, Sukumaran; Mangano, Carlo

    2014-01-01

    Purpose. Nowadays, the advancements in direct metal laser sintering (DMLS) technology allow the fabrication of titanium dental implants. The aim of this study was to evaluate implant survival, complications, and peri-implant marginal bone loss of DMLS implants used to support bar-retained maxillary overdentures. Materials and Methods. Over a 2-year period, 120 implants were placed in the maxilla of 30 patients (18 males, 12 females) to support bar-retained maxillary overdentures (ODs). Each OD was supported by 4 implants splinted by a rigid cobalt-chrome bar. At each annual follow-up session, clinical and radiographic parameters were assessed. The outcome measures were implant failure, biological and prosthetic complications, and peri-implant marginal bone loss (distance between the implant shoulder and the first visible bone-to-implant contact, DIB). Results. The 3-year implant survival rate was 97.4% (implant-based) and 92.9% (patient-based). Three implants failed. The incidence of biological complication was 3.5% (implant-based) and 7.1% (patient-based). The incidence of prosthetic complication was 17.8% (patient-based). No detrimental effects on marginal bone level were evidenced. Conclusions. The use of 4 DMLS titanium implants to support bar-retained maxillary ODs seems to represent a safe and successful procedure. Long-term clinical studies on a larger sample of patients are needed to confirm these results.

  7. Histological Evidence of the Osseointegration of Fractured Direct Metal Laser Sintering Implants Retrieved after 5 Years of Function.

    PubMed

    Mangano, Francesco; Mangano, Carlo; Piattelli, Adriano; Iezzi, Giovanna

    2017-01-01

    Direct metal laser sintering (DMLS) is an additive manufacturing technique that allows the fabrication of dental implants layer by layer through the laser fusion of titanium microparticles. The surface of DMLS implants is characterized by a high open porosity with interconnected pores of different sizes; therefore, it has the potential to enhance and accelerate bone healing. To date, however, there are no histologic/histomorphometric studies in the literature evaluating the interface between bone and DMLS implants in the long-term. To evaluate the interface between bone and DMLS implants retrieved after 5 years of functional loading. Two fractured DMLS implants were retrieved from the human jaws, using a 5 mm trephine bur. Both the implants were clinically stable and functioned regularly before fracture. The specimens were processed for histologic/histomorphometric evaluation; the bone-to-implant contact (BIC%) was calculated. Compact, mature lamellar bone was found over most of the DMLS implants in close contact with the implant surface; the histomorphometric evaluation showed a mean BIC% of 66.1% (±4.5%). The present histologic/histomorphometric study showed that DMLS implants were well integrated in bone, after 5 years of loading, with the peri-implant bone undergoing continuous remodeling at the interface.

  8. Accuracy evaluation of metal copings fabricated by computer-aided milling and direct metal laser sintering systems.

    PubMed

    Park, Jong-Kyoung; Lee, Wan-Sun; Kim, Hae-Young; Kim, Woong-Chul; Kim, Ji-Hwan

    2015-04-01

    To assess the marginal and internal gaps of the copings fabricated by computer-aided milling and direct metal laser sintering (DMLS) systems in comparison to casting method. Ten metal copings were fabricated by casting, computer-aided milling, and DMLS. Seven mesiodistal and labiolingual positions were then measured, and each of these were divided into the categories; marginal gap (MG), cervical gap (CG), axial wall at internal gap (AG), and incisal edge at internal gap (IG). Evaluation was performed by a silicone replica technique. A digital microscope was used for measurement of silicone layer. Statistical analyses included one-way and repeated measure ANOVA to test the difference between the fabrication methods and categories of measured points (α=.05), respectively. The mean gap differed significantly with fabrication methods (P<.001). Casting produced the narrowest gap in each of the four measured positions, whereas CG, AG, and IG proved narrower in computer-aided milling than in DMLS. Thus, with the exception of MG, all positions exhibited a significant difference between computer-aided milling and DMLS (P<.05). Although the gap was found to vary with fabrication methods, the marginal and internal gaps of the copings fabricated by computer-aided milling and DMLS fell within the range of clinical acceptance (<120 µm). However, the statistically significant difference to conventional casting indicates that the gaps in computer-aided milling and DMLS fabricated restorations still need to be further reduced.

  9. Maxillary Overdentures Supported by Four Splinted Direct Metal Laser Sintering Implants: A 3-Year Prospective Clinical Study

    PubMed Central

    Mangano, Francesco; Shibli, Jamil Awad; Anil, Sukumaran

    2014-01-01

    Purpose. Nowadays, the advancements in direct metal laser sintering (DMLS) technology allow the fabrication of titanium dental implants. The aim of this study was to evaluate implant survival, complications, and peri-implant marginal bone loss of DMLS implants used to support bar-retained maxillary overdentures. Materials and Methods. Over a 2-year period, 120 implants were placed in the maxilla of 30 patients (18 males, 12 females) to support bar-retained maxillary overdentures (ODs). Each OD was supported by 4 implants splinted by a rigid cobalt-chrome bar. At each annual follow-up session, clinical and radiographic parameters were assessed. The outcome measures were implant failure, biological and prosthetic complications, and peri-implant marginal bone loss (distance between the implant shoulder and the first visible bone-to-implant contact, DIB). Results. The 3-year implant survival rate was 97.4% (implant-based) and 92.9% (patient-based). Three implants failed. The incidence of biological complication was 3.5% (implant-based) and 7.1% (patient-based). The incidence of prosthetic complication was 17.8% (patient-based). No detrimental effects on marginal bone level were evidenced. Conclusions. The use of 4 DMLS titanium implants to support bar-retained maxillary ODs seems to represent a safe and successful procedure. Long-term clinical studies on a larger sample of patients are needed to confirm these results. PMID:25580124

  10. Comparison of conventional reconstruction plate versus direct metal laser sintering plate: an in vitro mechanical characteristics study.

    PubMed

    Xie, Pusheng; Ouyang, Hanbin; Deng, Yuping; Yang, Yang; Xu, Jing; Huang, Wenhua

    2017-09-02

    Additive manufacturing (AM) technology has helped to achieve several advances in the medical field, particularly as far as fabrication of implants is concerned. But the application of direct metal laser sintering (DMLS) bone plate is quite limited due to the indeterminate mechanical property. The purposes of this study were to characterize the biomechanical properties of the polished DMLS reconstruction plate and to compare these with the properties of commonly applied implants and to find whether the mechanical performance of DMLS plate meets the requirements for clinical application. In this study, we fabricated two groups of plates by DMLS and computer numerical control (CNC) techniques. After that, we polished all samples and investigated their roughness, components, hardness, static bending, and torsional performance. Moreover, cyclic bending tests and fractographic analysis were conducted. Statistical comparisons of the group by means of monotonic test data were made, and a qualitative comparison was performed to assess failures in fatigue. We found no differences in surface roughness or components after polishing, but the DMLS plate hardness is 7.42% (p < 0.01) greater than that of the CNC plates. Compared with the CNC plates, the DMLS plate static bending and torsional performance were significantly greater. In a dynamic test, the DMLS plates survived 10(6), 10(6), 32,731, and 33,264 cycles under 0.6, 0.8, 0.9, and 1 kN cyclic loads, respectively, while the CNC plates survived 10(6), 10(6), 10(6), and 283,714 cycles. These results indicate that the mechanical performances of the DMLS plate are stronger, and the strength under fatigue tests is sufficient. DMLS implant has great potential and may become a better choice for clinical use in the future. However, direct application of these AM instruments in the operating room requires further validation including animal and clinical experiment.

  11. Summary of Liquid Oxygen/Hydrogen, Direct Metal Laser Sintering Injector Testing and Evaluation Effort at Marshall Space Flight Center

    NASA Technical Reports Server (NTRS)

    Barnett, Gregory; Bullard, David B.

    2015-01-01

    The last several years have witnessed a significant advancement in the area of additive manufacturing technology. One area that has seen substantial expansion in application has been laser sintering (or melting) in a powder bed. This technology is often termed 3D printing or various acronyms that may be industry, process, or company specific. Components manufactured via 3D printing have the potential to significantly reduce development and fabrication time and cost. The usefulness of 3D printed components is influenced by several factors such as material properties and surface roughness. This paper details three injectors that were designed, fabricated, and tested in order to evaluate the utility of 3D printed components for rocket engine applications. The three injectors were tested in a hot-fire environment with chamber pressures of approximately 1400 psia. One injector was a 28 element design printed by Directed Manufacturing. The other two injectors were identical 40 element designs printed by Directed Manufacturing and Solid Concepts. All the injectors were swirl-coaxial designs and were subscale versions of a full-scale injector currently in fabrication. The test and evaluation programs for the 28 element and 40 element injectors provided a substantial amount of data that confirms the feasibility of 3D printed parts for future applications. The operating conditions of previously tested, conventionally manufactured injectors were reproduced in the 28 and 40 element programs in order to contrast the performance of each. Overall, the 3D printed injectors demonstrated comparable performance to the conventionally manufactured units. The design features of the aforementioned injectors can readily be implemented in future applications with a high degree of confidence.

  12. Catalytic direct asymmetric Michael reactions: taming naked aldehyde donors.

    PubMed

    Betancort, J M; Barbas, C F

    2001-11-15

    [reaction--see text] Direct catalytic enantio- and diastereoselective Michael addition reactions of unmodified aldehydes to nitro olefins using (S)-2-(morpholinomethyl)pyrrolidine as a catalyst are described. The reactions proceed in good yield (up to 96%) in a highly syn-selective manner (up to 98:2) with enantioselectivities approaching 80%. The resulting gamma-formyl nitro compounds are readily converted to chiral, nonracemic 3,4-disubstituted pyrrolidines.

  13. Microwave sintering process model.

    PubMed

    Peng, Hu; Tinga, W R; Sundararaj, U; Eadie, R L

    2003-01-01

    In order to simulate and optimize the microwave sintering of a silicon nitride and tungsten carbide/cobalt toolbits process, a microwave sintering process model has been built. A cylindrical sintering furnace was used containing a heat insulating layer, a susceptor layer, and an alumina tube containing the green toolbit parts between parallel, electrically conductive, graphite plates. Dielectric and absorption properties of the silicon nitride green parts, the tungsten carbide/cobalt green parts, and an oxidizable susceptor material were measured using perturbation and waveguide transmission methods. Microwave absorption data were measured over a temperature range from 20 degrees C to 800 degrees C. These data were then used in the microwave process model which assumed plane wave propagation along the radial direction and included the microwave reflection at each interface between the materials and the microwave absorption in the bulk materials. Heat transfer between the components inside the cylindrical sintering furnace was also included in the model. The simulated heating process data for both silicon nitride and tungsten carbide/cobalt samples closely follow the experimental data. By varying the physical parameters of the sintering furnace model, such as the thickness of the susceptor layer, the thickness of the allumina tube wall, the sample load volume and the graphite plate mass, the model data predicts their effects which are helpful in optimizing those parameters in the industrial sintering process.

  14. Enhanced Multiferroic Properties of YMnO3 Ceramics Fabricated by Spark Plasma Sintering Along with Low-Temperature Solid-State Reaction

    PubMed Central

    Wang, Meng; Wang, Ting; Song, Shenhua; Ravi, Muchakayala; Liu, Renchen; Ji, Shishan

    2017-01-01

    Based on precursor powders with a size of 200–300 nm prepared by the low-temperature solid-state reaction method, phase-pure YMnO3 ceramics are fabricated using spark plasma sintering (SPS). X-ray diffraction (XRD) and scanning electron microscopy (SEM) reveal that the high-purity YMnO3 ceramics can be prepared by SPS at 1000 °C for 5 minutes with annealing at 800 °C for 2 h. The relative density of the sample is as high as 97%, which is much higher than those of the samples sintered by other methods. The present dielectric and magnetic properties are much better than those of the samples fabricated by conventional methods and SPS with ball-milling precursors, and the ferroelectric loops at room temperature can be detected. These findings indicate that the YMnO3 ceramics prepared by the low temperature solid reaction method and SPS possess excellent dielectric lossy ferroelectric properties at room temperature, and magnetic properties at low temperature (10 K), making them suitable for potential multiferroic applications. PMID:28772832

  15. An evaluation of marginal fit of three-unit fixed dental prostheses fabricated by direct metal laser sintering system.

    PubMed

    Kim, Ki-Baek; Kim, Woong-Chul; Kim, Hae-Young; Kim, Ji-Hwan

    2013-07-01

    This in vitro study aimed to evaluate and compare marginal fit of three-unit fixed dental prostheses (FDPs) fabricated using a newly developed direct metal laser sintering (DMLS) system with that of three-unit FDPs by a conventional lost wax technique (LW) method. Ten cobalt-chromium alloy three-unit FDPs using DMLS system and another ten nickel-chromium alloy FDPs using LW method were fabricated. Marginal fit was examined using a light-body silicone. After setting, the silicon film was cut into four parts and the thickness of silicon layer was measured at 160× magnification using a digital microscope to measure absolute marginal discrepancy (AMD), marginal gap (MG) and internal gap (IG). A repeated measure ANOVA for statistical analysis was performed using the SPSS statistical package version 12.0 (α=0.05). The mean values of AMD, MG, and IG were significantly larger in the DMLS group than in the LW group (p<0.001). Means of AMD, MG and IG in the first molars were 83.3, 80.0, and 82.0μm in the LW group; and 128.0, 112.0, and 159.5μm in the DMLS group, respectively. No significant difference between measurements for premolars and molars was found (p>0.05). The marginal fit of the DMLS system appeared significantly inferior compared to that of the conventional LW method and slightly larger than the acceptable range. For clinical application further improvement of DMLS system may be required. Copyright © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  16. Histological and biomechanical analysis of porous additive manufactured implants made by direct metal laser sintering: a pilot study in sheep.

    PubMed

    Stübinger, Stefan; Mosch, Isabel; Robotti, Pierfrancesco; Sidler, Michéle; Klein, Karina; Ferguson, Stephen J; von Rechenberg, Brigitte

    2013-10-01

    It was the aim of this study to analyze osseointegrative properties of porous additive manufactured titanium implants made by direct metal laser sintering in a sheep model after an implantation period of 2 and 8 weeks. Three different types of implants were placed in the pelvis of six sheep. In each sheep were placed three standard machined (M), three sandblasted and etched (SE), and three porous additive manufactured (AM) implants. Of these three implants (one per type) were examined histologically and six implants were tested biomechanically. Additionally a semiquantitative histomorphometrical and qualitative fluorescent microscopic analysis were performed. After 2 and 8 weeks bone-to-implant-contact (BIC) values of the AM surface (2w: 20.49% ± 5.18%; 8w: 43.91% ± 9.69%) revealed no statistical significant differences in comparison to the M (2w: 20.33% ± 11.50%; 8w: 25.33% ± 4.61%) and SE (2w: 43.67 ± 12.22%; 8w: 53.33 ± 8.96%) surfaces. AM surface showed the highest increase of the BIC between the two observation time points. Considering the same implantation period histomorphometry and fluorescent labelling disclosed no significant differences in the bone surrounding the three implants groups. In contrast Removal-torque-test showed a significant improve in fixation strength (P ≤ 0.001) for the AM (1891.82 ± 308, 44 Nmm) surface after eight weeks in comparison to the M (198.93±88,04 Nmm) and SE (730.08 ± 151,89 Nmm) surfaces. All three surfaces (M, SE, and AM) showed sound osseointegration. AM implants may offer a possible treatment option in clinics for patients with compromised bone situations. Copyright © 2013 Wiley Periodicals, Inc., a Wiley Company.

  17. The influence of direct laser metal sintering implants on the early stages of osseointegration in diabetic mini-pigs.

    PubMed

    Tan, Naiwen; Liu, Xiangwei; Cai, Yanhui; Zhang, Sijia; Jian, Bo; Zhou, Yuchao; Xu, Xiaoru; Ren, Shuai; Wei, Hongbo; Song, Yingliang

    2017-01-01

    High failure rates of oral implants have been reported in diabetic patients due to the disruption of osseointegration. The aim of this study was to investigate whether direct laser metal sintering (DLMS) could improve osseointegration in diabetic animal models. Surface characterizations were carried out on two types of implants. Cell morphology and the osteogenic-related gene expression of MG63 cells were observed under conditions of DLMS and microarc oxidation (MAO). A diabetes model in mini-pigs was established by intravenous injection of streptozotocin (150 mg/kg), and a total of 36 implants were inserted into the mandibular region. Micro-computed tomography (micro-CT) and histologic evaluations were performed 3 and 6 months after implantation. The Ra (the average of the absolute height of all points) of MAO surface was 2.3±0.3 µm while the DLMS surface showed the Ra of 27.4±1.1 µm. The cells on DLMS implants spread out more podia than those on MAO implants through cell morphology analysis. Osteogenic-related gene expression was also dramatically increased in the DLMS group. Obvious improvement was observed in the micro-CT and Van Gieson staining analyses of DLMS implants compared with MAO at 3 months, although this difference disappeared by 6 months. DLMS implants showed a higher bone-implant contact percentage (33.2%±11.2%) at 3 months compared with MAO group (18.9%±7.3%) while similar results were showed at 6 months between DLMS group (42.8%±10.1%) and MAO group (38.3%±10.8%). The three-dimensional environment of implant surfaces with highly porous and fully interconnected channel and pore architectures can improve cell spreading and accelerate the progress of osseointegration in diabetic mini-pigs.

  18. Comparison of fracture resistance between cast, CAD/CAM milling, and direct metal laser sintering metal post systems.

    PubMed

    Bilgin, Mehmet Selim; Erdem, Ali; Dilber, Erhan; Ersoy, İbrahim

    2016-01-01

    The purpose of this study was to compare the fracture resistance of Co-Cr post-cores fabricated with 3 different techniques: traditional casting (TC), computer-aided design and manufacturing (CAD/CAM) milling (CCM) and direct metal laser sintering (DMLS). Forty intact human mandibular premolar were endodontically treated. The roots were then randomly divided into four groups according to the post systems: the control group was only filled with gutta percha. Co-Cr metal posts were fabricated with TC, CCM and DMLS in the other three groups. The posts were luted with a resin cement and subjected to compression test at a crosshead speed of 1mm/min. The statistical analysis of the data was performed using one-way analysis of variance (ANOVA) and multiple comparison post hoc Tukey tests (α=.05). The samples were examined under a stereomicroscope with ×20 magnification for the evaluation of the fracture types. The mean fracture loads were 432.69 N for control, 608.89 N for TC, 689.40 N for DMLS and 959.26 N for CCM. One-way ANOVA revealed significant difference between the groups (p<0.01). In the post hoc Tukey test, there were significant differences between groups except DMLS and TC. While Co-Cr posts fabricated by TC and DMLS systems performed similarly in terms of fracture resistance, posts fabricated by CCM techniques showed higher fracture resistance values. Co-Cr metal posts fabricated by CCM and DMLS could be an alternative to TC processing in daily clinical application. Copyright © 2015 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

  19. The influence of direct laser metal sintering implants on the early stages of osseointegration in diabetic mini-pigs

    PubMed Central

    Tan, Naiwen; Liu, Xiangwei; Cai, Yanhui; Zhang, Sijia; Jian, Bo; Zhou, Yuchao; Xu, Xiaoru; Ren, Shuai; Wei, Hongbo; Song, Yingliang

    2017-01-01

    Background High failure rates of oral implants have been reported in diabetic patients due to the disruption of osseointegration. The aim of this study was to investigate whether direct laser metal sintering (DLMS) could improve osseointegration in diabetic animal models. Methods Surface characterizations were carried out on two types of implants. Cell morphology and the osteogenic-related gene expression of MG63 cells were observed under conditions of DLMS and microarc oxidation (MAO). A diabetes model in mini-pigs was established by intravenous injection of streptozotocin (150 mg/kg), and a total of 36 implants were inserted into the mandibular region. Micro-computed tomography (micro-CT) and histologic evaluations were performed 3 and 6 months after implantation. Results The Ra (the average of the absolute height of all points) of MAO surface was 2.3±0.3 µm while the DLMS surface showed the Ra of 27.4±1.1 µm. The cells on DLMS implants spread out more podia than those on MAO implants through cell morphology analysis. Osteogenic-related gene expression was also dramatically increased in the DLMS group. Obvious improvement was observed in the micro-CT and Van Gieson staining analyses of DLMS implants compared with MAO at 3 months, although this difference disappeared by 6 months. DLMS implants showed a higher bone–implant contact percentage (33.2%±11.2%) at 3 months compared with MAO group (18.9%±7.3%) while similar results were showed at 6 months between DLMS group (42.8%±10.1%) and MAO group (38.3%±10.8%). Conclusion The three-dimensional environment of implant surfaces with highly porous and fully interconnected channel and pore architectures can improve cell spreading and accelerate the progress of osseointegration in diabetic mini-pigs. PMID:28814861

  20. Microstructure and DC electrical conductivity of spinel nickel ferrite sintered in air and nitrogen atmospheres

    SciTech Connect

    Liu, Baogang; Zhou, Kechao; Li, Zhiyou; Zhang, Dou; Zhang, Lei

    2010-11-15

    In recent years, the development of inert anode materials has gained considerable attention because such materials are capable of producing only environment-friendly O{sub 2} and saving energy during aluminum electrolysis. Nickel ferrite was prepared by a solid-state reaction as the inert anode in this study and its microstructures and direct current conductivities were analyzed in detail regarding the effects of different sintering atmospheres. A single-phase spinel structure was confirmed for all samples by X-ray powder diffraction. The grain sizes and the relative densities of the samples sintered in nitrogen increased by over 7 {mu}m and 10.8%, respectively, compared to those sintered in air. The direct current conductivities of the samples sintered in nitrogen showed a drastic increase compared to those sintered in air, believed to be due to the effects of increased Fe{sup 2+} ion concentration at octahedral sites and the increase of the relative density.

  1. Directional sensitivity of "first trial" reactions in human balance control.

    PubMed

    Oude Nijhuis, Lars B; Allum, John H J; Borm, George F; Honegger, Flurin; Overeem, Sebastiaan; Bloem, Bastiaan R

    2009-06-01

    Support-surface movements are commonly used to examine balance control. Subjects typically receive a series of identical or randomly interspersed multidirectional balance perturbations and the atypical "first trial reaction" (evoked by the first perturbation) is often excluded from further analysis. However, this procedure may obscure vital information about neurophysiological mechanisms associated with the first perturbation and, by analogy, fully unexpected falls. We studied first trial reactions, aiming to clarify their directional impact on postural control and to characterize the underlying neurophysiological substrate. We instructed 36 subjects to maintain balance following support-surface rotations in six different directions. Perturbations in each direction were delivered in blocks, consisting of 10 serial stimuli. Full body kinematics, surface reactive forces, and electromyographic (EMG) responses were recorded. Regardless of direction, for the very first rotation, displacement of the center of mass was 15% larger compared with the ensuing nine identical rotations (P < 0.0001). This first trial reaction immediately reemerged whenever a new perturbation direction was introduced. First trial reactions (and near-falls) were greatest for backward-directed rotations and smallest for laterally directed rotations. This directional dependence coincided with early changes in vertical head accelerations. First trial reactions in EMG responses involved larger amplitudes in general and earlier muscle response onsets in upper body muscles. These findings show that first trial reactions are associated with significantly increased postural instability, mainly due to increased response amplitudes. Although rapid habituation occurs following presentation of identical stimuli, subjects immediately become unstable again when the perturbation direction suddenly changes. Excessive responses due to a failure to combine proprioceptive and vestibular cues effectively may explain

  2. Ceramic Sintering

    DTIC Science & Technology

    1975-07-01

    PERFORMING ORGANIZATION NAME AND ADDRESS General Electric Company Corporate Research and Development Schenectady, New York 12301 10...Sintering For preparation of the sintering specimens, the powders were dispersed in a l/206 benzene solution of an organic pressing aid and in some...N00019-72-0129, Naval Air Systems Command. 10. G. Busch and H. Labhart, "Über bed Mechanismus ber Elektrischen Leit- Fahigkeit des Silicium Carbids

  3. SINTERING METHOD

    DOEpatents

    Googin, J.M.

    1963-11-01

    Methods of making articles by powder metallurgy techniques are presented. An article is made by packing a metal powder into a desired shape, raising the temperature of the powder compact to a sintering temperature in the presence of a reducing gas, and alternately increasing and decreasing the pressure of the gas while the temperatume is being raised. The product has a greater density than can be achieved by sintering for the same length of time at a constant gas pressure. (AEC)

  4. Fundamental studies of retrograde reactions in direct liquefaction

    SciTech Connect

    Serio, M.A.; Solomon, P.R.; Bassilakis, R.; Kroo, E.

    1989-01-01

    Most of the proposed processing schemes for improving liquefaction yields involve favoring bond-breaking and radical stabilization reactions over the retrograde reactions. The retrograde reactions are often encountered before liquefaction temperatures are reached. The objective of this program is to elucidate and model the retrograde reaction chemistry in direct coal liquefaction through the application of experimental techniques and theoretical models which have been successfully employed at Advanced Fuel Research (AFR) and SRI International (a subcontractor) to understand and predict coal reaction behavior. The study of retrograde reactions is being done using an integrated approach using extensive characterization of the liquefaction chemistry of three kinds of systems: (1) model polymers; (2) coal; and (3) modified coals.

  5. Revisiting and computing reaction coordinates with Directional Milestoning.

    PubMed

    Kirmizialtin, Serdal; Elber, Ron

    2011-06-16

    The method of Directional Milestoning is revisited. We start from an exact and more general expression and state the conditions and validity of the memory-loss approximation. An algorithm to compute a reaction coordinate from Directional Milestoning data is presented. The reaction coordinate is calculated as a set of discrete jumps between Milestones that maximizes the flux between two stable states. As an application we consider a conformational transition in solvated adenosine. We compare a long molecular dynamic trajectory with Directional Milestoning and discuss the differences between the maximum flux path and minimum energy coordinates. © 2011 American Chemical Society

  6. Direct studies of (α,p) reactions with HELIOS

    NASA Astrophysics Data System (ADS)

    Lai, Jianping; Blackmon, J. C.; Deibel, C. M.; Dimarco, D.; Gardiner, H.; Lauer, A.; Santiago-Gonzalez, D.; Williams, C.; Digiovine, B.; Greene, J.; Rohrer, J.; Helios Group At Argonne National Lab Collaboration

    2014-09-01

    In a variety of astrophysical processes, (α,p) type reactions have significant effects on final energy output and elemental abundances. However, only a handful of reactions have been measured due to technical limitations. Innovative new equipment and techniques, therefore, are necessary to extend measurement limits of these reactions rates. The HELIcal Orbit Spectrometer(HELIOS), serves as an important tool in studying reactions using radioactive ion beams at the Argonne Tandem Linac Accelerator System facility. With a specially designed gas target, we are able to study (α,p) reaction directly. HELIOS can separate protons from reactions with different energy states and the heavy recoils can be detected in coincidence by a high efficiency gas ionization detector. This combination has been successful in our pilot experiments. A series of (α,p) experiments using this setup in HELIOS are planned. We will start with 20Ne(α,p), which is crucial in Type Ia supernovae. A direct measurement of 30S(α,p), a key reaction in X ray burst, is also included in the near future plans and the beam development of 30S is in progress. Preliminary results will be presented. In a variety of astrophysical processes, (α,p) type reactions have significant effects on final energy output and elemental abundances. However, only a handful of reactions have been measured due to technical limitations. Innovative new equipment and techniques, therefore, are necessary to extend measurement limits of these reactions rates. The HELIcal Orbit Spectrometer(HELIOS), serves as an important tool in studying reactions using radioactive ion beams at the Argonne Tandem Linac Accelerator System facility. With a specially designed gas target, we are able to study (α,p) reaction directly. HELIOS can separate protons from reactions with different energy states and the heavy recoils can be detected in coincidence by a high efficiency gas ionization detector. This combination has been successful in our pilot

  7. Recent Direct Reaction Experimental Studies with Radioactive Tin Beams

    DOE PAGES

    Jones, K. L.; Ahn, S.; Allmond, J. M.; ...

    2015-01-01

    Direct reaction techniques are powerful tools to study the single-particle nature of nuclei. Performing direct reactions on short-lived nuclei requires radioactive ion beams produced either via fragmentation or the Isotope Separation OnLine (ISOL) method. Some of the most interesting regions to study with direct reactions are close to the magic numbers where changes in shell structure can be tracked. These changes can impact the final abundances of explosive nucleosynthesis. The structure of the chain of tin isotopes is strongly influenced by the Z = 50 proton shell closure, as well as the neutron shell closures lying in the neutron-rich, Nmore » = 82, and neutron-deficient, N = 50, regions. Here, we present two examples of direct reactions on exotic tin isotopes. The first uses a one-neutron transfer reaction and a low-energy reaccelerated ISOL beam to study states in Sn-131 from across the N = 82 shell closure. The second example utilizes a one-neutron knockout reaction on fragmentation beams of neutron-deficient Sn-106,108Sn. In conclusion, In both cases, measurements of γ rays in coincidence with charged particles proved to be invaluable.« less

  8. Recent Direct Reaction Experimental Studies with Radioactive Tin Beams

    SciTech Connect

    Jones, K. L.; Ahn, S.; Allmond, J. M.; Ayres, A.; Bardayan, D. W.; Baugher, T.; Bazin, D.; Berryman, J. S.; Bey, A.; Bingham, C.; Cartegni, L.; Cerizza, G.; Chae, K. Y.; Cizewski, J. A.; Gade, A.; Galindo-Uribarri, A.; Garcia-Ruiz, R. F.; Grzywacz, R.; Howard, M. E.; Kozub, R. L.; Liang, J. F.; Manning, B.; Matoš, M.; McDaniel, S.; Miller, D.; Nesaraja, C. D.; O'Malley, P. D.; Padgett, S.; Padilla-Rodal, E.; Pain, S. D.; Pittman, S. T.; Radford, D. C.; Ratkiewicz, A.; Schmitt, K. T.; Shore, A.; Smith, M. S.; Stracener, D. W.; Stroberg, S. R.; Tostevin, J.; Varner, R. L.; Weisshaar, D.; Wimmer, K.; Winkler, R.

    2015-01-01

    Direct reaction techniques are powerful tools to study the single-particle nature of nuclei. Performing direct reactions on short-lived nuclei requires radioactive ion beams produced either via fragmentation or the Isotope Separation OnLine (ISOL) method. Some of the most interesting regions to study with direct reactions are close to the magic numbers where changes in shell structure can be tracked. These changes can impact the final abundances of explosive nucleosynthesis. The structure of the chain of tin isotopes is strongly influenced by the Z = 50 proton shell closure, as well as the neutron shell closures lying in the neutron-rich, N = 82, and neutron-deficient, N = 50, regions. Here, we present two examples of direct reactions on exotic tin isotopes. The first uses a one-neutron transfer reaction and a low-energy reaccelerated ISOL beam to study states in Sn-131 from across the N = 82 shell closure. The second example utilizes a one-neutron knockout reaction on fragmentation beams of neutron-deficient Sn-106,108Sn. In conclusion, In both cases, measurements of γ rays in coincidence with charged particles proved to be invaluable.

  9. Direct catalytic enantio- and diastereoselective aldol reaction of thioamides.

    PubMed

    Iwata, Mitsutaka; Yazaki, Ryo; Chen, I-Hon; Sureshkumar, Devarajulu; Kumagai, Naoya; Shibasaki, Masakatsu

    2011-04-13

    A direct catalytic asymmetric aldol reaction of thioamides using a soft Lewis acid/hard Brønsted base cooperative catalyst comprising (R,R)-Ph-BPE/[Cu(CH(3)CN)(4)]PF(6)/LiOAr is described. Exclusive enolate generation from thioacetamides through a soft-soft interaction with the soft Lewis acid allowed for a direct aldol reaction to α-nonbranched aliphatic aldehydes, which are usually susceptible to self-condensation under conventional basic conditions. A hard Lewis basic phosphine oxide has emerged as an effective additive to constitute a highly active ternary soft Lewis acid/hard Brønsted base/hard Lewis base cooperative catalyst, enabling a direct enantio- and diastereoselective aldol reaction of thiopropionamides. Strict control of the amount of the hard Lewis base was essential to drive the catalytic cycle efficiently with a minimized retro-aldol pathway, affording syn-aldol products with high stereoselectivity. Divergent transformation of the thioamide functionality is an obvious merit of the present aldol methodology, allowing for a facile transformation of the aldol product into the corresponding aldehyde, ketone, amide, amine, and ketoester. An aldehyde derived from the direct aldol reaction was subjected to a second direct aldol reaction, which proceeded in a catalyst-controlled manner to provide 1,3-diols with high stereoselectivity. © 2011 American Chemical Society

  10. In Situ Al Based Composites Fabricated in Al-SiO2-C System by Reaction Sintering

    NASA Astrophysics Data System (ADS)

    Mokhnache, El Oualid; Wang, Guisong; Geng, Lin; Kaveendran, Balasubramaniam; Henniche, Abdelkhalek; Ramdani, Noureddine

    2015-07-01

    In situ Al-based composites with different SiO2/C/Al molar ratios were fabricated by reaction hot pressing. Differential scanning calorimetry (DSC) was used to investigate the reaction mechanisms in the Al-SiO2-C system. X-ray diffraction results revealed that no new resultant phase was observed below the melting temperature of aluminum except the SiO2, C and Al phases. Heating at different synthesis temperatures showed that, up to 1000°C with a holding time of 1 h, the reactions in the Al-SiO2-C system took place completely, where the final products were Al2O3, SiC, Al4C3 and Si. Microstructural observation showed that the in situ synthesized Al2O3, SiC, Al4C3, and Si were dispersed uniformly and had fine sizes less than 2 µm. The formed interfaces between the reinforcements and Al matrix are clean and free from any interfacial phase. During cooling, the synthesized Si formed a multilayer growth in the (111) direction. When the SiO2/C/Al molar ratio was (6/3/9), more Al2O3 and Si were produced along with the complete prevention of Al4C3 in the Al-SiO2-C system. The yield strength, ultimate tensile strength and Brinell hardness of the in situ fabricated composites are significantly higher than those of pure aluminum matrix, with a decrease of ductility. Mechanisms governing the tensile fracture process are also discussed.

  11. Organoaluminum-mediated direct cross-coupling reactions.

    PubMed

    Minami, Hiroki; Saito, Tatsuo; Wang, Chao; Uchiyama, Masanobu

    2015-04-07

    We present a direct cross-coupling reaction between arylaluminum compounds (ArAlMe2 ⋅LiCl) and organic halides RX (R=aryl, alkenyl, alkynyl; X=I, Br, and Cl) without any external catalyst. The reaction takes place smoothly, simply upon heating, thereby enabling the efficient and chemo-/stereoselective formation of biaryl, alkene, and alkyne coupling products with broad functional group compatibility.

  12. Direct measurements of radiative capture reactions with DRAGON

    NASA Astrophysics Data System (ADS)

    Christian, Gregory

    2015-10-01

    Direct measurements of radiative proton and alpha capture reactions are crucial for understanding nucleosynthesis in a variety of astrophysical environments, including classical novae, supernovae, X-Ray bursts, and quiescent stellar burning. Often the most important reactions have very low cross sections or involve unstable targets, making laboratory measurements extremely challenging. The detector of recoils and gammas of nuclear reactions (DRAGON) at TRIUMF is a recoil mass separator designed to measure radiative capture reactions in inverse kinematics, with beam suppression factors as high as 1016. When combined with the intense radioactive beams available at the ISAC-I facility, DRAGON's capabilities are unique and world-leading. In this talk, I will give a brief technical overview of DRAGON before presenting results from recent experiments. Some highlights include the first-ever direct measurement of 38K(p , γ) 39Ca, a crucial reaction for determining the endpoint of nova nucleosynthesis, and measurements of 76Se(α , γ) 80Kr. The latter measurements determine the rate of the reverse reaction, 80Kr(γ , α) 76Se, an important waiting point in the synthesis of the p-nuclei. I will also discuss future (and ongoing) developments at DRAGON, including the commissioning of a new chamber for high-precision elastic scattering measurements and plans to determine the 330 keV resonance strength in 18F(p , γ) 19Ne via measurements of 15O(α , γ) 19Ne and 15O + α elastic scattering.

  13. Direct reactions for nuclear structure required for fundamental symmetry tests

    NASA Astrophysics Data System (ADS)

    Garrett, P. E.; Rand, E. T.; Diaz Varela, A.; Ball, G. C.; Bildstein, V.; Faestermann, T.; Hadinia, B.; Hertenberger, R.; Jamieson, D. S.; Jigmeddorj, B.; Leach, K. G.; Svensson, C. E.; Wirth, H.-F.

    2016-09-01

    A program of nuclear structure studies to support fundamental symmetry tests has been initiated. Motivated by the search for an electric dipole moment in 199Hg, the structure in the vicinity has been explored via direct reaction studies. To date, these have included the 198,200Hg(d, d') inelastic scattering reactions, with the aim to obtain information on the E2 and E3 strength distributions, and the 198Hg(d, p) and 200Hg(d, t) reactions to obtain information on the single-particle states in 199Hg. The studies using the 200Hg targets have been fully analyzed using the FRESCO reaction code yielding the E2 and E3 strength distribution to 4 MeV in excitation energy, and the (d, t) single- particle strength to over 3 MeV in excitation energy.

  14. Fabrication of Al matrix composite reinforced with submicrometer-sized Al2O3 particles formed by combustion reaction between HEMM Al and V2O5 composite particles during sintering

    NASA Astrophysics Data System (ADS)

    Woo, Kee Do; Kim, Jae Hwang; Kwon, Eui Pyo; Moon, Min Seok; Lee, Hyun Bom; Sato, Tatsuo; Liu, Zhiguang

    2010-04-01

    To fabricate an Al-V matrix composite reinforced with submicron-sized Al2O3 and AlxVy (Al3V, Al10V) phases, high energy mechanical milling (HEMM) and sintering were employed. By increasing the milling time, the size of mechanically milled powder was significantly reduced. In this study, the average powder size of 59 μm for Al, and 178 μm for V2O5 decreased with the formation of a new product, Al-Al2O3-AlxVy, with a size range from 1.3 μm to 2.6 μm formed by the in-situ combustion reaction during sintering of HEM milled Al and V2O5 composite powders. The in-situ reaction between Al and V2O5 during the HEMM and sintering transformed the Al2O3 and AlxVy (Al3V, Al10V) phases. Most of the reduced V reacted with excess the Al to form AlxVy (Al3V, Al10V) with very little V dissolved into Al matrix. By increasing the milling time and weight percentage of V2O5, the hardness of the Al-Al2O3-AlxVy composite sintered at 1173 K increased. The composite fabricated with the HEMM Al-20wt.%V2O5 composite powder and sintering at 1173 K for 2 h had the highest hardness.

  15. From Powders to Dense Metal Parts: Characterization of a Commercial AlSiMg Alloy Processed through Direct Metal Laser Sintering.

    PubMed

    Manfredi, Diego; Calignano, Flaviana; Krishnan, Manickavasagam; Canali, Riccardo; Ambrosio, Elisa Paola; Atzeni, Eleonora

    2013-03-06

    In this paper, a characterization of an AlSiMg alloy processed by direct metal laser sintering (DMLS) is presented, from the analysis of the starting powders, in terms of size, morphology and chemical composition, through to the evaluation of mechanical and microstructural properties of specimens built along different orientations parallel and perpendicular to the powder deposition plane. With respect to a similar aluminum alloy as-fabricated, a higher yield strength of about 40% due to the very fine microstructure, closely related to the mechanisms involved in this additive process is observed.

  16. From Powders to Dense Metal Parts: Characterization of a Commercial AlSiMg Alloy Processed through Direct Metal Laser Sintering

    PubMed Central

    Manfredi, Diego; Calignano, Flaviana; Krishnan, Manickavasagam; Canali, Riccardo; Ambrosio, Elisa Paola; Atzeni, Eleonora

    2013-01-01

    In this paper, a characterization of an AlSiMg alloy processed by direct metal laser sintering (DMLS) is presented, from the analysis of the starting powders, in terms of size, morphology and chemical composition, through to the evaluation of mechanical and microstructural properties of specimens built along different orientations parallel and perpendicular to the powder deposition plane. With respect to a similar aluminum alloy as-fabricated, a higher yield strength of about 40% due to the very fine microstructure, closely related to the mechanisms involved in this additive process is observed. PMID:28809344

  17. Direct measurements of astrophysically important α-induced reactions

    NASA Astrophysics Data System (ADS)

    Avila, Melina

    2016-03-01

    Understanding stellar evolution is one of the primary objectives of nuclear astrophysics. Reaction rates involving α-particles are often key nuclear physics inputs in stellar models. For instance, there are numerous (α , p) reactions fundamental for the understanding of X-ray bursts and the production of 44Ti in core-collapse supernovae. Furthermore, some (α , n) reactions are considered as one of the main neutron sources in the s-process. However, direct measurements of these reactions at relevant astrophysical energies are experimentally challenging because of their small cross section and intensity limitation of radioactive beams. The active target system MUSIC offers a unique opportunity to study (α , p) and (α , n) reactions because its segmented anode allows the investigation of a large energy range in the excitation function with a single measurement. Recent results on the direct measurement of (α , n) and (α , p) measurements in the MUSIC detector will be discussed. This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Nuclear Physics, under Contract Number DE-AC02-06CH11357. This research used resources of ANL's ATLAS facility, which is a DOE Office of Science User.

  18. Degradation of artificial sweeteners via direct and indirect photochemical reactions.

    PubMed

    Perkola, Noora; Vaalgamaa, Sanna; Jernberg, Joonas; Vähätalo, Anssi V

    2016-07-01

    We studied the direct and indirect photochemical reactivity of artificial sweeteners acesulfame, saccharin, cyclamic acid and sucralose in environm entally relevant dilute aqueous solutions. Aqueous solutions of sweeteners were irradiated with simulated solar radiation (>290 nm; 96 and 168 h) or ultraviolet radiation (UVR; up to 24 h) for assessing photochemical reactions in surface waters or in water treatment, respectively. The sweeteners were dissolved in deionised water for examination of direct photochemical reactions. Direct photochemical reactions degraded all sweeteners under UVR but only acesulfame under simulated solar radiation. Acesulfame was degraded over three orders of magnitude faster than the other sweeteners. For examining indirect photochemical reactions, the sweeteners were dissolved in surface waters with indigenous dissolved organic matter or irradiated with aqueous solutions of nitrate (1 mg N/L) and ferric iron (2.8 mg Fe/L) introduced as sensitizers. Iron enhanced the photodegradation rates but nitrate and dissolved organic matter did not. UVR transformed acesulfame into at least three products: iso-acesulfame, hydroxylated acesulfame and hydroxypropanyl sulfate. Photolytic half-life was one year for acesulfame and more than several years for the other sweeteners in surface waters under solar radiation. Our study shows that the photochemical reactivity of commonly used artificial sweeteners is variable: acesulfame may be sensitive to photodegradation in surface waters, while saccharin, cyclamic acid and sucralose degrade very slowly even under the energetic UVR commonly used in water treatment.

  19. [Cardiovascular reactions to gravitational force in different directions].

    PubMed

    Xue, Y Y; Liu, G Y; Xie, B S; Cheng, X Y; Wang, Y C

    2000-04-01

    To observe the features of the cardiovascular reactions to gravitational forces along different axes of the body. Dogs were exposed to gravitational forces along axes of body on an animal centrifuge. It was found that when the direction of G force changed from +Gz to +Gx, the predominating effect on the cardiovascular system changed from the drop of eye level blood pressure to the increase of central venous pressure, and the reactions of the organism changed from a presson reflex of the arterial system to the inhibition of cardiac activities at higher G levels. The turning point was found to be at the back angle of 75 degrees with respect to the direction of the gravitational force. These findings provide an important reference for choosing the optimal seat back angle in a manned space vehicle.

  20. Enantioselective direct aldol reactions catalyzed by l-prolinamide derivatives

    PubMed Central

    Tang, Zhuo; Jiang, Fan; Cui, Xin; Gong, Liu-Zhu; Mi, Ai-Qiao; Jiang, Yao-Zhong; Wu, Yun-Dong

    2004-01-01

    l-Prolinamides 2, prepared from l-proline and simple aliphatic and aromatic amines, have been found to be active catalysts for the direct aldol reaction of 4-nitrobenzaldehyde with neat acetone at room temperature. They give moderate enantioselectivities of up to 46% enantiomeric excess (ee). The enantioselectivity increases as the amide N—H becomes a better hydrogen bond donor. l-Prolinamides 3, derived from the reaction of l-proline with α,β-hydroxyamines such that there is a terminal hydroxyl group, show more efficient catalysis and higher enantioselectivities. In particular, catalyst 3h, prepared from l-proline and (1S,2S)-diphenyl-2-aminoethanol, exhibits high enantioselectivities of up to 93% ee for aromatic aldehydes and up to >99% ee for aliphatic aldehydes under –25°C. Model reactions of benzaldehyde with three enamines derived from the condensation of prolinamides with acetone have been studied by quantum mechanics calculations. The calculations reveal that the amide N—H and the terminal hydroxyl groups form hydrogen bonds with the benzaldehyde substrate. These hydrogen bonds reduce the activation energy and cause high enantioselectivity. Our results suggest a new strategy in the design of new organic catalysts for direct asymmetric aldol reactions and related transformations. PMID:15079057

  1. Missing facial parts computed by a morphable model and transferred directly to a polyamide laser-sintered prosthesis: an innovation study.

    PubMed

    Mueller, A A; Paysan, P; Schumacher, R; Zeilhofer, H-F; Berg-Boerner, B-I; Maurer, J; Vetter, T; Schkommodau, E; Juergens, P; Schwenzer-Zimmerer, K

    2011-12-01

    Mirroring of missing facial parts and rapid prototyping of templates have become widely used in the manufacture of prostheses. However, mirroring is not applicable for central facial defects, and the manufacture of a template still requires labour-intensive transformation into the final facial prosthesis. We have explored innovative techniques to meet these remaining challenges. We used a morphable model of a face for the reconstruction of missing facial parts that did not have mirror images, and skin-coloured polyamide laser sintering for direct manufacture of the prosthesis. From the knowledge gleaned from a data set of 200 coloured, three-dimensional scans, we generated a missing nose that was statistically compatible with the remaining parts of the patient's face. The planned prosthesis was manufactured directly from biocompatible skin-coloured polyamide powder by selective laser sintering, and the prosthesis planning system produced a normal-looking reconstruction. The polyamide will need adjustable colouring, and we must be able to combine it with a self-curing resin to fulfil the requirements of realistic permanent use. Copyright © 2011 The British Association of Oral and Maxillofacial Surgeons. Published by Elsevier Ltd. All rights reserved.

  2. SinterHab

    NASA Astrophysics Data System (ADS)

    Rousek, Tomáš; Eriksson, Katarina; Doule, Ondřej

    2012-05-01

    This project describes a design study for a core module on a Lunar South Pole outpost, constructed by 3D printing technology with the use of in-situ resources and equipped with a bio-regenerative life support system. The module would be a hybrid of deployable (CLASS II) and in-situ built (CLASS III) structures. It would combine deployable membrane structures and pre-integrated rigid elements with a sintered regolith shell for enhanced radiation and micrometeorite shielding. The closed loop ecological system would support a sustainable presence on the Moon with particular focus on research activities. The core module accommodates from four to eight people, and provides laboratories as a test bed for development of new lunar technologies directly in the environment where they will be used. SinterHab also includes an experimental garden for development of new bio-regenerative life support system elements. The project explores these various concepts from an architectural point-of-view particularly, as they constitute the building, construction and interior elements. The construction method for SinterHab is based on 3D printing by sintering of the lunar regolith. Sinterator robotics 3D printing technology proposed by NASA JPL enables construction of future generations of large lunar settlements with little imported material and the use of solar energy. The regolith is processed, placed and sintered by the Sinterator robotics system which combines the NASA ATHLETE and the Chariot remotely controlled rovers. Microwave sintering creates a rigid structure in the form of walls, vaults and other architectural elements. The interior is coated with a layer of inflatable membranes inspired by the TransHab project. The life-support system is mainly bio-regenerative and several parts of the system are intrinsically multifunctional and serve more than one purpose. The plants for food production are also an efficient part of atmosphere revitalization and water treatment. Moreover

  3. Direct Measurement of the ^11C(,)^14N Reaction

    NASA Astrophysics Data System (ADS)

    Hayakawa, S.; Kubono, S.; Yamaguchi, H.; Hashimoto, T.; Binh, D. N.; Kahl, D.; Wakabayashi, Y.; Iwasa, N.; Kume, N.; Miura, Y.; Teranishi, T.; He, J. J.; Kwon, Y. K.; Komatsubara, T.; Kato, S.; Wanajo, S.

    2009-10-01

    A recent simulation of the rp-process in neutrino-driven winds in type II supernovae (νp-process) suggests that the ^11C(,)^14N reaction could be an important breakout pass from the pp-chain region to the CNO region. However, there are only very limited experimental information of the reaction cross section available from the time-reverse reaction studies. In order to determine the reaction rate of ^11C(,)^14N, a direct measurement by means of the thick-target inverse-kinematics method has recently been performed using low-energy ^11C beams from the CNS Radioactive Ion Beam (CRIB) separator, a ^4He gas target and δE-E position-sensitive silicon telescopes at three downstream angles. The experiment covered ECM = 0.5-5 MeV corresponding to the stellar temperature of 1.5-7GK. The obtained reaction cross section including some resonances and transitions to the excited states of ^14N will be reported.

  4. Directed long-range molecular migration energized by surface reaction

    NASA Astrophysics Data System (ADS)

    Harikumar, K. R.; Polanyi, John C.; Zabet-Khosousi, Amir; Czekala, Piotr; Lin, Haiping; Hofer, Werner A.

    2011-05-01

    The recoil of adsorbates away (desorption) and towards (reaction) surfaces is well known. Here, we describe the long-range recoil of adsorbates in the plane of a surface, and accordingly the novel phenomenon of reactions occurring at a substantial distance from the originating event. Three thermal and three electron-induced surface reactions are shown by scanning tunnelling microscopy to propel their physisorbed ethylenic products across the rough surface of Si(100) over a distance of up to 200 Å before an attachment reaction. The recoil energy in the ethylenic products comes from thermal exoergicity or from electronic excitation of chemisorbed alkenes. We propose that the mechanism of migration is a rolling motion, because the recoiling molecule overcomes raised surface obstacles. Electronic excitation of propene causes directional recoil and often end-to-end inversion, suggesting cartwheeling. Ab initio calculations of the halogenation and electron-induced reactions support a model in which asymmetric forces between the molecule and the surface induce rotation and therefore migration.

  5. Directed long-range molecular migration energized by surface reaction.

    PubMed

    Harikumar, K R; Polanyi, John C; Zabet-Khosousi, Amir; Czekala, Piotr; Lin, Haiping; Hofer, Werner A

    2011-05-01

    The recoil of adsorbates away (desorption) and towards (reaction) surfaces is well known. Here, we describe the long-range recoil of adsorbates in the plane of a surface, and accordingly the novel phenomenon of reactions occurring at a substantial distance from the originating event. Three thermal and three electron-induced surface reactions are shown by scanning tunnelling microscopy to propel their physisorbed ethylenic products across the rough surface of Si(100) over a distance of up to 200 Å before an attachment reaction. The recoil energy in the ethylenic products comes from thermal exoergicity or from electronic excitation of chemisorbed alkenes. We propose that the mechanism of migration is a rolling motion, because the recoiling molecule overcomes raised surface obstacles. Electronic excitation of propene causes directional recoil and often end-to-end inversion, suggesting cartwheeling. Ab initio calculations of the halogenation and electron-induced reactions support a model in which asymmetric forces between the molecule and the surface induce rotation and therefore migration.

  6. Histological reaction of sintered nanohydroxyapatite-coated cuff and its fibroblast-like cell hybrid for an indwelling catheter.

    PubMed

    Furuzono, Tsutomu; Ueki, Mitsuki; Kitamura, Harumi; Oka, Kazumasa; Imai, Enyu

    2009-04-01

    Rapid tissue-ingrowth of a sintered hydroxyapatite(HAp)-coated and cell-hybrid subcutaneous cuff equipped with an indwelling catheter was developed. The rod-like HAp nanoparticles were coated by covalent bonding on the surface of the silk fibroin (SF) fibers for about 100 microm of the length. The fibers were transplanted three-dimensionally on a cuff substrate made of silicone elastomer with an adhesive. The fibroblast-like cells, explanted and proliferated from skin tissue containing the epidermis, dermis, and subcutaneous tissue of Japanese white rabbits, were incubated on the three-dimensional cuff for three days. Three types of cuff--polyester, HAp-coated, and cell-hybrid cuffs--were percutaneously implanted into the backs of the same animals for 3 and 7 days. The subcutaneous tissues around the cuffs were stained with hematoxylin-eosin. Immunohistochemical staining to identify macrophages and alpha-smooth muscle actin (alpha-SMA) was also done and examined by light microscopy. The alpha-SMA-positive area was very limited in the polyester cuff group even after 7 days, although many macrophages infiltrated into the fibers. In the cell-hybrid cuff group, on the other hand, an alpha-SMA-positive area was formed extensively after 3 and 7 days, causing severe inflammation. In the HAp-coated cuff group, an alpha-SMA-positive area was formed among the fibers with little inflammation. The extent order of the alpha-SMA-positive area was cell-hybrid cuff > HAp-coated cuff > polyester cuff, while the degree of inflammatory cells order was cell-hybrid cuff > polyester cuff > HAp-coated cuff.

  7. Additive manufacturing technology (direct metal laser sintering) as a novel approach to fabricate functionally graded titanium implants: preliminary investigation of fabrication parameters.

    PubMed

    Lin, Wei-Shao; Starr, Thomas L; Harris, Bryan T; Zandinejad, Amirali; Morton, Dean

    2013-01-01

    This article describes the preliminary findings of the mechanical properties of functionally graded titanium with controlled distribution of porosity and a reduced Young's modulus on the basis of a computeraided design (CAD) file, using the rapid-prototyping, direct metal laser sintering (DMLS) technique. Sixty specimens of Ti-6Al-4V were created using a DMLS machine (M270) following the standard for tensile testing of metals. One group was fabricated with only 170 W of laser energy to create fully dense specimens (control group). The remaining specimens all featured an outer fully dense "skin" layer and a partially sintered porous inner "core" region. The outer "skin" of each specimen was scanned at 170 W and set at a thickness of 0.35, 1.00, or 1.50 mm for different specimen groups. The inner "core" of each specimen was scanned at a lower laser power (43 or 85 W). The partially sintered core was clearly visible in all specimens, with somewhat greater porosity with the lower laser power. However, the amount of porosity in the core region was not related to the laser power alone; thinner skin layers resulted in higher porosity for the same power values in the core structure. The lowest Young's modulus achieved, 35 GPa, is close to that of bone and was achieved with a laser power of 43 W and a skin thickness of 0.35 mm, producing a core that comprised 74% of the total volume. Additive manufacturing technology may provide an efficient alternative way to fabricate customized dental implants based on a CAD file with a functionally graded structure that may minimize stress shielding and improve the long-term performance of dental implants.

  8. MgAl2O4(001) based magnetic tunnel junctions made by direct sputtering of a sintered spinel target

    NASA Astrophysics Data System (ADS)

    Belmoubarik, Mohamed; Sukegawa, Hiroaki; Ohkubo, Tadakatsu; Mitani, Seiji; Hono, Kazuhiro

    2016-03-01

    We developed a fabrication process of an epitaxial MgAl2O4 barrier for magnetic tunnel junctions (MTJs) using a direct sputtering method from an MgAl2O4 spinel sintered target. Annealing the sputter-deposited MgAl2O4 layer sandwiched between Fe electrodes led to the formation of a (001)-oriented cation-disorder spinel with atomically sharp interfaces and lattice-matching with the Fe electrodes. A large tunnel magnetoresistance ratio up to 245% at 297 K (436% at 3 K) was achieved in the Fe/MgAl2O4/Fe(001) MTJ as well as an excellent bias voltage dependence. These results indicate that the direct sputtering is an alternative method for the realization of high performance MTJs with a spinel-based tunnel barrier.

  9. MgAl{sub 2}O{sub 4}(001) based magnetic tunnel junctions made by direct sputtering of a sintered spinel target

    SciTech Connect

    Belmoubarik, Mohamed; Sukegawa, Hiroaki Ohkubo, Tadakatsu; Mitani, Seiji; Hono, Kazuhiro

    2016-03-28

    We developed a fabrication process of an epitaxial MgAl{sub 2}O{sub 4} barrier for magnetic tunnel junctions (MTJs) using a direct sputtering method from an MgAl{sub 2}O{sub 4} spinel sintered target. Annealing the sputter-deposited MgAl{sub 2}O{sub 4} layer sandwiched between Fe electrodes led to the formation of a (001)-oriented cation-disorder spinel with atomically sharp interfaces and lattice-matching with the Fe electrodes. A large tunnel magnetoresistance ratio up to 245% at 297 K (436% at 3 K) was achieved in the Fe/MgAl{sub 2}O{sub 4}/Fe(001) MTJ as well as an excellent bias voltage dependence. These results indicate that the direct sputtering is an alternative method for the realization of high performance MTJs with a spinel-based tunnel barrier.

  10. Mechanical properties of (Bi,Sb)2Te3 solid solutions obtained by directional crystallization and spark plasma sintering

    NASA Astrophysics Data System (ADS)

    Lavrent'ev, M. G.; Osvenskii, V. B.; Pivovarov, G. I.; Sorokin, A. I.; Bulat, L. P.; Bublik, V. T.; Tabachkova, N. Yu.

    2016-01-01

    We have studied the temperature dependence of the mechanical strength at uniaxial compression for solid solutions based on bismuth and antimony chalcogenides, which were prepared by three methods: (i) vertical zone melting (VZM), (ii) hot extrusion, and (iii) spark plasma sintering (SPS). In the samples of solid solutions obtained by VZM and extrusion, a brittle-ductile transition was observed in a wised temperature interval of 200-350°C. In nanostructured SPS samples, transition from brittle to plastic fracture was observed within 170-200°C. The room-temperature strength of nanostructured samples was eight to nine times as large as that of VZM samples, and the stress-strain curves of these materials were significantly different. At a temperature of about 300°C, the strength of nanostructured solid solutions decreases to nearly zero.

  11. Effect of process parameters on hardness, temperature profile and solidification of different layers processed by direct metal laser sintering (DMLS)

    NASA Astrophysics Data System (ADS)

    Ahmed, Sazzad Hossain; Mian, Ahsan; Srinivasan, Raghavan

    2016-07-01

    In DMLS process objects are fabricated layer by layer from powdered material by melting induced by a controlled laser beam. Metallic powder melts and solidifies to form a single layer. Solidification map during layer formation is an important route to characterize micro-structure and grain morphology of sintered layer. Generally, solidification leads to columnar, equiaxed or mixture of these two types grain morphology depending on solidification rate and thermal gradient. Eutectic or dendritic structure can be formed in fully equiaxed zone. This dendritic growth has a large effect on material properties. Smaller dendrites generally increase ductility of the layer. Thus, materials can be designed by creating desired grain morphology in certain regions using DMLS process. To accomplish this, hardness, temperature distribution, thermal gradient and solidification cooling rate in processed layers will be studied under change of process variables by using finite element analysis, with specific application to Ti-6Al-4V.

  12. Effect of process parameters on hardness, temperature profile and solidification of different layers processed by direct metal laser sintering (DMLS)

    SciTech Connect

    Ahmed, Sazzad Hossain; Mian, Ahsan Srinivasan, Raghavan

    2016-07-12

    In DMLS process objects are fabricated layer by layer from powdered material by melting induced by a controlled laser beam. Metallic powder melts and solidifies to form a single layer. Solidification map during layer formation is an important route to characterize micro-structure and grain morphology of sintered layer. Generally, solidification leads to columnar, equiaxed or mixture of these two types grain morphology depending on solidification rate and thermal gradient. Eutectic or dendritic structure can be formed in fully equiaxed zone. This dendritic growth has a large effect on material properties. Smaller dendrites generally increase ductility of the layer. Thus, materials can be designed by creating desired grain morphology in certain regions using DMLS process. To accomplish this, hardness, temperature distribution, thermal gradient and solidification cooling rate in processed layers will be studied under change of process variables by using finite element analysis, with specific application to Ti-6Al-4V.

  13. Direct reaction experimental studies with beams of radioactive tin ions

    SciTech Connect

    Jones, K. L. Ayres, A.; Bey, A.; Burcher, S.; Cartegni, L.; Cerizza, G.; Ahn, S.; Allmond, J. M.; Beene, J. R.; Galindo-Uribarri, A.; Liang, J. F.; Nesaraja, C. D.; Pain, S. D.; Radford, D. C.; Schmitt, K. T.; Smith, M. S.; Stracener, D. W.; Varner, R. L.; Bardayan, D. W.; Baugher, T.; and others

    2015-10-15

    The tin chain of isotopes provides a unique region in which to investigate the evolution of single-particle structure, spreading from N = 50 at {sup 100}Sn, through 10 stable isotopes and the N = 82 shell closure at {sup 132}Sn out into the r-process path. Direct reactions performed on radioactive ion beams are sensitive spectroscopic tools for studying exotic nuclei. Here we present one experiment knocking out neutrons from tin isotopes that are already neutron deficient and two reactions that add a neutron to neutron-rich {sup 130}Sn. Both techniques rely on selective particle identification and the measurement of γ rays in coincidence with charged ions. We present the goals of the two experiments and the particle identification for the channels of interest. The final results will be presented in future publications.

  14. Template directed reactions of 2-aminoadenylic acid derivatives

    NASA Technical Reports Server (NTRS)

    Webb, T. R.; Orgel, L. E.

    1982-01-01

    The template-directed oligomerization of activated derivatives of 2-aminoadenylic acid (paA) on polyuridylic acid (poly(U)) in aqueous buffers was studied. The reaction differs from that of adenylic acid (pA) under identical conditions, in that only di- and tri-nucleotides are observed as substantial products rather than a longer sequence of oligomers. The reaction of paA also differs from that of pA in that it does not require Mg (2+), and is less susceptible to increased temperature. The relevance of these observations to the chemical evolution of polynucleotide replication is discussed. Improved syntheses of paA and its diphosphate are reported.

  15. Template directed reactions of 2-aminoadenylic acid derivatives

    NASA Technical Reports Server (NTRS)

    Webb, T. R.; Orgel, L. E.

    1982-01-01

    The template-directed oligomerization of activated derivatives of 2-aminoadenylic acid (paA) on polyuridylic acid (poly(U)) in aqueous buffers was studied. The reaction differs from that of adenylic acid (pA) under identical conditions, in that only di- and tri-nucleotides are observed as substantial products rather than a longer sequence of oligomers. The reaction of paA also differs from that of pA in that it does not require Mg (2+), and is less susceptible to increased temperature. The relevance of these observations to the chemical evolution of polynucleotide replication is discussed. Improved syntheses of paA and its diphosphate are reported.

  16. Direct Reaction Experimental Studies with Beams of Radioactive Tin Ions

    SciTech Connect

    Jones, K. L.; Ahn, S.H.; Allmond, James M; Ayres, A.; Bardayan, Daniel W; Baugher, T.; Bazin, D.; Beene, James R; Berryman, J. S.; Bey, A.; Bingham, C. R.; Cartegni, L.; Chae, K. Y.; Gade, A.; Galindo-Uribarri, Alfredo {nmn}; Garcia-Ruiz, R.F.; Grzywacz, Robert Kazimierz; Howard, Meredith E; Kozub, R. L.; Liang, J Felix; Manning, Brett M; Matos, M.; McDaniel, S.; Miller, D.; Nesaraja, Caroline D; O'Malley, Patrick; Padgett, S; Padilla-Rodal, Elizabeth; Pain, Steven D; Pittman, S. T.; Radford, David C; Ratkiewicz, Andrew J; Schmitt, Kyle; Smith, Michael Scott; Stracener, Daniel W; Stroberg, S.; Tostevin, Jeffrey A; Varner Jr, Robert L; Weisshaar, D.; Wimmer, K.

    2015-01-01

    The tin chain of isotopes provides a unique region in which to investigate the evolution of single-particle structure, spreading from N = 50 at Sn-100, through 10 stable isotopes and the N = 82 shell closure at Sn-132 out into the r-process path. Direct reactions performed on radioactive ion beams are sensitive spectroscopic tools for studying exotic nuclei. Here we present one experiment knocking out neutrons from tin isotopes that are already neutron deficient and two reactions that add a neutron to neutron-rich Sn-130. Both techniques rely on selective particle identification and the measurement of gamma rays in coincidence with charged ions. We present the goals of the two experiments and the particle identification for the channels of interest. The final results will be presented in future publications.

  17. The charge transfer transition phenomenon and microstructure of Eu{sup 3+}-doped NaCaPO{sub 4} phosphors sintered with NH{sub 4}Cl flux via solid-state reaction

    SciTech Connect

    Peng, Yu-Ming; Su, Yan-Kuin; Yang, Ru-Yuan

    2013-05-15

    Graphical abstract: This paper describes: The charge transfer transition phenomenon and microstructure of Eu{sup 3+}-doped NaCaPO{sub 4} phosphors sintered with NH{sub 4}Cl flux via solid-state reaction. The emission intensity of NaCa{sub 0.95}PO{sub 4}:0.05Eu{sup 3+} phosphors with 2 wt.% NH{sub 4}Cl flux is enhanced as the sintering temperature was increased from 800 °C to 1000 °C and reveals the maximum value at 1000 °C. Photoluminescence emission spectra of NaCa{sub 0.95}PO{sub 4}:0.05Eu{sup 3+} phosphors with 2 wt.% NH{sub 4}Cl flux sintered at various sintering temperature for 3 h via solid state reaction method (λ{sub ex} = 270 nm). Highlights: ► NH{sub 4}Cl flux is helpful for enhancing the crystallization degree and decreasing surface defects. ► A single phase of NaCaPO{sub 4}:Eu{sup 3+} phosphor was observed as the sintering temperature was increased from 800 °C to 1000 °C. ► The intensity of the excitation peaks displays a maximum value at 1000 °C. ► The NaCaPO{sub 4} host added with NH{sub 4}Cl flux and sintered at the different temperature can affect the morphology. ► The NaCaPO{sub 4} host added with NH{sub 4}Cl flux and sintered at the different temperature can affect fluorescent properties. - Abstract: NaCa{sub 0.95}PO{sub 4}:0.05Eu{sup 3+} phosphors with 2 wt.% NH{sub 4}Cl flux sintered at various sintering temperature (800, 900, 1000, 1100 °C) for 3 h under air atmosphere were synthesized successfully via solid state reaction method. It is found that the addition of NH{sub 4}Cl flux and different sintering temperatures can affect the morphology and fluorescent properties of NaCa{sub 0.95}PO{sub 4}:0.05Eu{sup 3+} phosphor. The X-ray diffractions show a single phase and the microstructure observations show uniform morphologies for NaCa{sub 0.95}PO{sub 4}:0.05Eu{sup 3+} phosphors sintered at the range from 900 °C to 1000 °C, indicating that addition of 2 wt.% NH{sub 4}Cl flux is helpful for enhancing the crystallization, thus

  18. Direct Catalytic Asymmetric Mannich-Type Reaction of Alkylamides.

    PubMed

    Arteaga, Fernando Arteaga; Liu, Zijian; Brewitz, Lennart; Chen, Jianyang; Sun, Bo; Kumagai, Naoya; Shibasaki, Masakatsu

    2016-05-20

    Direct enolate formation coupled with subsequent enantioselective C-C bond formation remains a topic of intense interest in asymmetric catalysis. This methodology is achieved even with low acidic amides without an electron-withdrawing group at the α-position in the context of a Mannich-type reaction. Acetate-, propionate-, and butyrate-type 7-azaindoline amides served as enolate precursors to afford the desired Mannich adducts with high stereoselectivity, and ligand-enabled diastereo-divergency provided access to both anti/syn diastereomers. The facile transformation of the amide moiety ensures the synthetic utility of the Mannich adducts.

  19. The Effect of Sintering Temperature on the Formation of (Tl, Cr)-1212 Superconducting Ceramic from Coprecipitated Oxalate Precursors

    SciTech Connect

    Hamadneh, Imad; Hui, Lee Teik; Shukor, Roslan Abd

    2007-05-09

    TlSr1212 superconductors were synthesized by solid-state reaction using Tl-containing precursor powder prepared by coprecipitation of metal acetates with stoichiometric ratio based on Tl0.85Cr0.15Sr2CaCu2O7-{delta} composition. The samples were sintered at temperatures between 960 and 980 deg. C for duration of 5 minutes. XRD patterns for samples sintered at 960 deg. C showed formation of dominant 1212 phase in addition to minor 1201 phase and SrCO3 impurity. At this sintering temperature, the best superconducting behavior with TC(R= 0) of 100 K was observed for the sample sintered at 970 deg. C. SEM investigations on the sample revealed elongated grains which belong to 1212 phase with a slight directional grain alignment. The sample with sintering temperature of 960 deg. C showed better grains connection as compared to the rest of the samples.

  20. Scanning electron microscopy (SEM) and X-ray dispersive spectrometry evaluation of direct laser metal sintering surface and human bone interface: a case series.

    PubMed

    Mangano, Carlo; Piattelli, Adriano; Raspanti, Mario; Mangano, Francesco; Cassoni, Alessandra; Iezzi, Giovanna; Shibli, Jamil Awad

    2011-01-01

    Recent studies have shown that direct laser metal sintering (DLMS) produces structures with complex geometry and consequently that allow better osteoconductive properties. The aim of this patient report was to evaluate the early bone response to DLMS implant surface retrieved from human jaws. Four experimental DLMS implants were inserted in the posterior mandible of four patients during conventional dental implant surgery. After 8 weeks, the micro-implants and the surrounding tissue were removed and prepared for scanning electron microscopy (SEM) and histomorphometric analysis to evaluate the bone-implant interface. The SEM and EDX evaluations showed a newly formed tissue composed of calcium and phosphorus. The bone-to-implant contact presented a mean of 60.5 ± 11.6%. Within the limits of this patient report, data suggest that the DLMS surfaces presented a close contact with the human bone after a healing period of 8 weeks.

  1. Effect of Process Parameter on Barium Titanate Stannate (BTS) Materials Sintered at Low Sintering

    NASA Astrophysics Data System (ADS)

    Shukla, Alok; Bajpai, P. K.

    2011-11-01

    Ba(Ti1-xSnx)O3 solid solutions with (x = 0.15, 0.20, 0.30 and 0.40) are synthesized using conventional solid state reaction method. Formation of solid solutions in the range 0 ≤ x ≤0.40 is confirmed using X-ray diffraction technique. Single phase solid solutions with homogeneous grain distribution are observed at relatively low sintering by controlling process parameters viz. sintering time. Composition at optimized temperature (1150 °C) sintered by varying the sintering time, stabilize in cubic perovskite phase. The % experimental density increase with increasing the time of sintering instead of increasing sintering temperature. The lattice parameter increases by increasing the tin composition in the material. This demonstrates that process parameter optimization can lead to single phase at relatively lower sintering-a major advantage for the materials used as capacitor element in MLCC.

  2. Clinical acceptability of metal-ceramic fixed partial dental prosthesis fabricated with direct metal laser sintering technique-5 year follow-up.

    PubMed

    Prabhu, Radhakrishnan; Prabhu, Geetha; Baskaran, Eswaran; Arumugam, Eswaran M

    2016-01-01

    In recent years, direct metal laser sintered (DMLS) metal-ceramic-based fixed partial denture prostheses have been used as an alternative to conventional metal-ceramic fixed partial denture prostheses. However, clinical studies for evaluating their long-term clinical survivability and acceptability are limited. The aim of this study was to assess the efficacy of metal-ceramic fixed dental prosthesis fabricated with DMLS technique, and its clinical acceptance on long-term clinical use. The study group consisted of 45 patients who were restored with posterior three-unit fixed partial denture prosthesis made using direct laser sintered metal-ceramic restorations. Patient recall and clinical examination of the restorations were done after 6months and every 12 months thereafter for the period of 60 months. Clinical examination for evaluation of longevity of restorations was done using modified Ryge criteria which included chipping of the veneered ceramic, connector failure occurring in the fixed partial denture prosthesis, discoloration at the marginal areas of the veneered ceramic, and marginal adaptation of the metal and ceramic of the fixed denture prosthesis. Periapical status was assessed using periodical radiographs during the study period. Survival analysis was made using the Kaplan-Meier method. None of the patients had failure of the connector of the fixed partial denture prostheses during the study period. Two exhibited biological changes which included periapical changes and proximal caries adjacent to the abutments. DMLS metal-ceramic fixed partial denture prosthesis had a survival rate of 95.5% and yielded promising results during the 5-year clinical study.

  3. High-performance direct conversion X-ray detectors based on sintered hybrid lead triiodide perovskite wafers

    NASA Astrophysics Data System (ADS)

    Shrestha, Shreetu; Fischer, René; Matt, Gebhard J.; Feldner, Patrick; Michel, Thilo; Osvet, Andres; Levchuk, Ievgen; Merle, Benoit; Golkar, Saeedeh; Chen, Haiwei; Tedde, Sandro F.; Schmidt, Oliver; Hock, Rainer; Rührig, Manfred; Göken, Mathias; Heiss, Wolfgang; Anton, Gisela; Brabec, Christoph J.

    2017-07-01

    Lead halide perovskite semiconductors are in general known to have an inherently high X-ray absorption cross-section and a significantly higher carrier mobility than any other low-temperature solution-processed semiconductor. So far, the processing of several-hundred-micrometres-thick high-quality crystalline perovskite films over a large area has been unresolved for efficient X-ray detection. In this Article, we present a mechanical sintering process to fabricate polycrystalline methyl ammonium lead triiodide perovskite (MAPbI3) wafers with millimetre thickness and well-defined crystallinity. Benchmarking of the MAPbI3 wafers against state-of-the-art CdTe detectors reveals competitive conversion efficiencies of 2,527 µC Gyair-1 cm-2 under 70 kVp X-ray exposure. The high ambipolar mobility-lifetime product of 2 × 10-4 cm2 V-1 is suggested to be responsible for this exceptionally high sensitivity. Our findings inform a new generation of highly efficient and low-cost X-ray detectors based on perovskite wafers.

  4. Direct Measurement of Mercury Reactions In Coal Power Plant Plumes

    SciTech Connect

    Leonard Levin

    2005-12-31

    Recent field and pilot-scale results indicate that divalent mercury emitted from power plants may rapidly transform to elemental mercury within the power plant plumes. Simulations of mercury chemistry in plumes based on measured rates to date have improved regional model fits to Mercury Deposition Network wet deposition data for particular years, while not degrading model verification fits for remaining years of the ensemble. The years with improved fit are those with simulated deposition in grid cells in the State of Pennsylvania that have matching MDN station data significantly less than the model values. This project seeks to establish a full-scale data basis for whether or not significant reduction or oxidation reactions occur to mercury emitted from coal-fired power plants, and what numerical redox rate should apply for extension to other sources and for modeling of power plant mercury plumes locally, regionally, and nationally. Although in-stack mercury (Hg) speciation measurements are essential to the development of control technologies and to provide data for input into atmospheric fate and transport models, the determination of speciation in a cooling coal combustion plume is more relevant for use in estimating Hg fate and effects through the atmosphere. It is mercury transformations that may occur in the plume that determine the eventual rate and patterns of mercury deposited to the earth's surface. A necessary first step in developing a supportable approach to modeling any such transformations is to directly measure the forms and concentrations of mercury from the stack exit downwind to full dispersion in the atmosphere. As a result, a study was sponsored by EPRI and jointly funded by EPRI, the U.S Department of Energy (DOE), and the Wisconsin Department of Administration. The study was designed to further our understanding of plume chemistry. The study was carried out at the We Energies Pleasant Prairie Power Plant, Pleasant Prairie, Wisconsin, just

  5. Correlations probed in direct two-nucleon removal reactions

    SciTech Connect

    Simpson, E. C.; Tostevin, J. A.

    2010-10-15

    Final-state-exclusive momentum distributions of fast, forward-traveling residual nuclei, following two-nucleon removal from fast secondary radioactive beams of projectile nuclei, can and have now been measured. Assuming that the most important reaction mechanism is the sudden direct removal of a pair of nucleons from a set of relatively simple, active shell-model orbital configurations, such distributions were predicted to depend strongly on the total angular momentum I carried by the two nucleons--the final-state spin for spin 0{sup +} projectiles. The sensitivity of these now-accessible observables to specific details of the (correlated) two-nucleon wave functions is of importance. We clarify that it is the total orbital angular momentum L of the two nucleons that is the primary factor in determining the shapes and widths of the calculated momentum distributions. It follows that, with accurate measurements, this dependence upon the L makeup of the two-nucleon wave functions could be used to assess the accuracy of (shell- or many-body-) model predictions of these two-nucleon configurations. By using several tailored examples, with specific combinations of active two-nucleon orbitals, we demonstrate that more-subtle structure aspects may be observed, allowing such reactions to probe and/or confirm the details of theoretical model wave functions.

  6. Correlations probed in direct two-nucleon removal reactions

    NASA Astrophysics Data System (ADS)

    Simpson, E. C.; Tostevin, J. A.

    2010-10-01

    Final-state-exclusive momentum distributions of fast, forward-traveling residual nuclei, following two-nucleon removal from fast secondary radioactive beams of projectile nuclei, can and have now been measured. Assuming that the most important reaction mechanism is the sudden direct removal of a pair of nucleons from a set of relatively simple, active shell-model orbital configurations, such distributions were predicted to depend strongly on the total angular momentum I carried by the two nucleons—the final-state spin for spin 0+ projectiles. The sensitivity of these now-accessible observables to specific details of the (correlated) two-nucleon wave functions is of importance. We clarify that it is the total orbital angular momentum L of the two nucleons that is the primary factor in determining the shapes and widths of the calculated momentum distributions. It follows that, with accurate measurements, this dependence upon the L makeup of the two-nucleon wave functions could be used to assess the accuracy of (shell- or many-body-) model predictions of these two-nucleon configurations. By using several tailored examples, with specific combinations of active two-nucleon orbitals, we demonstrate that more-subtle structure aspects may be observed, allowing such reactions to probe and/or confirm the details of theoretical model wave functions.

  7. Optical and biological properties of transparent nanocrystalline hydroxyapatite obtained through spark plasma sintering.

    PubMed

    Li, Zhong; Thompson, Brianna C; Dong, Zhili; Khor, Khiam Aik

    2016-12-01

    Transparent bioceramics have attracted a large amount of research interest as they facilitate direct observation of biointerfacial reactions. Thus far, attempts to achieve transparent hydroxyapatite have been focused on augmenting the sintering pressure and/or extending the sintering duration. This study aims at fabricating transparent HA using a direct and fast spark plasma sintering process with appropriate starting powder and moderate sintering pressure. Three types of raw powder, namely micro-spheres, nano-rods and nano-spheres, were sintered to investigate the optical and biological properties of the compacted pellets. It was found that in terms of transparency, the micro-sphere pellet sintered at 1000°C stood out with an in-line transmittance as high as 84% achieved at 1300nm for a 2mm thick sample. In addition, pellets fabricated from micro-spheres demonstrated the highest cell viability in in vitro biological tests with L929 cells. Living cells cultured on a transparent micro-sphere pellet could be directly and clearly observed by light microscopy. It is thus concluded that the micro-sphere powder is the most desirable raw material to manufacture transparent hydroxyapatite because it could enable dense pellets with notably high transparency and outstanding in vitro biocompatibility to be readily obtained.

  8. Evaluation of marginal/internal fit of chrome-cobalt crowns: Direct laser metal sintering versus computer-aided design and computer-aided manufacturing.

    PubMed

    Gunsoy, S; Ulusoy, M

    2016-01-01

    The purpose of this study was to evaluate the internal and marginal fit of chrome cobalt (Co-Cr) crowns were fabricated with laser sintering, computer-aided design (CAD) and computer-aided manufacturing, and conventional methods. Polyamide master and working models were designed and fabricated. The models were initially designed with a software application for three-dimensional (3D) CAD (Maya, Autodesk Inc.). All models were fabricated models were produced by a 3D printer (EOSINT P380 SLS, EOS). 128 1-unit Co-Cr fixed dental prostheses were fabricated with four different techniques: Conventional lost wax method, milled wax with lost-wax method (MWLW), direct laser metal sintering (DLMS), and milled Co-Cr (MCo-Cr). The cement film thickness of the marginal and internal gaps was measured by an observer using a stereomicroscope after taking digital photos in ×24. Best fit rates according to mean and standard deviations of all measurements was in DLMS both in premolar (65.84) and molar (58.38) models in μm. A significant difference was found DLMS and the rest of fabrication techniques (P < 0.05). No significant difference was found between MCo-CR and MWLW in all fabrication techniques both in premolar and molar models (P > 0.05). DMLS was best fitting fabrication techniques for single crown based on the results.The best fit was found in marginal; the larger gap was found in occlusal.All groups were within the clinically acceptable misfit range.

  9. Development of an in-situ multi-component reinforced Al-based metal matrix composite by direct metal laser sintering technique — Optimization of process parameters

    SciTech Connect

    Ghosh, Subrata Kumar; Bandyopadhyay, Kaushik; Saha, Partha

    2014-07-01

    In the present investigation, an in-situ multi-component reinforced aluminum based metal matrix composite was fabricated by the combination of self-propagating high-temperature synthesis and direct metal laser sintering process. The different mixtures of Al, TiO{sub 2} and B{sub 4}C powders were used to initiate and maintain the self-propagating high-temperature synthesis by laser during the sintering process. It was found from the X-ray diffraction analysis and scanning electron microscopy that the reinforcements like Al{sub 2}O{sub 3}, TiC, and TiB{sub 2} were formed in the composite. The scanning electron microscopy revealed the distribution of the reinforcement phases in the composite and phase identities. The variable parameters such as powder layer thickness, laser power, scanning speed, hatching distance and composition of the powder mixture were optimized for higher density, lower porosity and higher microhardness using Taguchi method. Experimental investigation shows that the density of the specimen mainly depends upon the hatching distance, composition and layer thickness. On the other hand, hatching distance, layer thickness and laser power are the significant parameters which influence the porosity. The composition, laser power and layer thickness are the key influencing parameters for microhardness. - Highlights: • The reinforcements such as Al{sub 2}O{sub 3}, TiC, and TiB{sub 2} were produced in Al-MMC through SHS. • The density is mainly influenced by the material composition and hatching distance. • Hatching distance is the major influencing parameter on porosity. • The material composition is the significant parameter to enhance the microhardness. • The SEM micrographs reveal the distribution of TiC, TiB{sub 2} and Al{sub 2}O{sub 3} in the composite.

  10. Direct enantioselective aldol reactions catalyzed by a proline-thiourea host-guest complex.

    PubMed

    Reis, Omer; Eymur, Serkan; Reis, Barbaros; Demir, Ayhan S

    2009-03-07

    Proline-thiourea host-guest complex-catalyzed direct enantioselective aldol reactions have been developed, in which the catalytic activities were evaluated in the direct asymmetric aldol reactions of various aromatic aldehydes and cyclohexanone.

  11. Comparative analysis on surface property in anodic oxidation polishing of reaction-sintered silicon carbide and single-crystal 4H silicon carbide

    NASA Astrophysics Data System (ADS)

    Shen, Xinmin; Tu, Qunzhang; Deng, Hui; Jiang, Guoliang; He, Xiaohui; Liu, Bin; Yamamura, Kazuya

    2016-04-01

    For effective machining of difficult-to-machine materials, such as reaction-sintered silicon carbide (RS-SiC) and single-crystal 4H silicon carbide (4H-SiC), a novel polishing technique named anodic oxidation polishing was proposed, which combined with the anodic oxidation of substrate and slurry polishing of oxide. By scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM-EDX) observation and atomic force microscopy analysis, both the anodic oxidation behaviors of RS-SiC and 4H-SiC were investigated. Through comparison of the surfaces before and after hydrofluoric acid etching of the oxidized samples by the scanning white light interferometry (SWLI) measurement, the relationships between oxidation depth and oxidation time were obtained, and the calculated oxidation rate for RS-SiC was 5.3 nm/s and that for 4H-SiC was 5.8 nm/s based on the linear Deal-Grove model. Through anodic oxidation polishing of RS-SiC substrate and 4H-SiC substrate, respectively, the surface roughness rms obtained by SWLI was improved to 2.103 nm for RS-SiC and to 0.892 nm for 4H-SiC. Experimental results indicate that anodic oxidation polishing is an effective method for the machining of RS-SiC and 4H-SiC samples, which would improve the process level of SiC substrates and promote the application of SiC products in the fields of optics, ceramics, semiconductors, electronics, and so on.

  12. On the Mechanism of Oxazoline-Directed Metalations: Evidence for Nitrogen-Directed Reactions.

    PubMed

    Sammakia, Tarek; Latham, Hallie A.

    1996-03-08

    We recently described a method for the synthesis of ferrocene complexes possessing planar chirality which relies on the asymmetric deprotonation of chiral ferrocenyloxazolines. The unexpected stereochemical outcome of these reactions led us to examine whether the metalation is directed by the oxygen or the nitrogen of the oxazoline. In this paper, we describe the synthesis of a constrained ferrocenyloxazoline (compound 13) in which oxygen- and nitrogen-directed metalations provide different stereochemical outcomes. Our results show that nitrogen is responsible for the directive effects of the oxazoline when alkyllithium reagents are used to deprotonate the ferrocene. The implications of this result on the origin of asymmetric induction in the metalation of the unconstrained ferrocenyloxazolines 19 and 20 are discussed.

  13. Enabling direct nanoscale observations of biological reactions with dynamic TEM

    SciTech Connect

    Evans, James E.; Browning, Nigel D.

    2013-02-18

    Biological processes can occur over a wide range of spatial and temporal scales; from femtoseconds to hours and from angstroms to meters. Although no single experimental method can fully cover this entire phase space, many new biological insights can be expected from a better understanding of the processes that occur on the very fast timescales and very small length scales. In this regard, new instruments that use fast x-ray or electron pulses are now available that are expected to reveal new mechanistic insights for macromolecular protein dynamics. To ensure that any observed conformational change is physiologically relevant and not constrained by three-dimensional crystal packing, it would be preferable for experiments to utilize smaller protein samples such as single particles or two-dimensional crystals that mimic the target protein’s native environment. These samples aren’t typically amenable to x-ray analysis, but transmission electron microscopy has successfully imaged such sample geometries for over 40 years and permits data acquisition using both direct imaging and diffraction modes. While conventional transmission electron microscopes (TEM) have only visualized biological samples with atomic resolution in an arrested or frozen state, the recent development of the dynamic TEM (DTEM) extends electron microscopy capabilities into dynamics. A new 2nd generation DTEM that is currently being constructed has the potential to observe live biological processes with unprecedented spatiotemporal resolution by using pulsed electron packets to probe the sample on the micro- and nanosecond timescale. In addition to the enhanced temporal resolution, the DTEM also operates in the pump-probe regime that can permit visualizing reactions propagating in real-time. This article reviews the experimental parameters necessary for coupling DTEM with in situ liquid microscopy to allow direct imaging of protein conformational dynamics in a fully hydrated environment.

  14. Enabling direct nanoscale observations of biological reactions with dynamic TEM

    PubMed Central

    Evans, James E.; Browning, Nigel D.

    2013-01-01

    Biological processes occur on a wide range of spatial and temporal scales: from femtoseconds to hours and from angstroms to meters. Many new biological insights can be expected from a better understanding of the processes that occur on these very fast and very small scales. In this regard, new instruments that use fast X-ray or electron pulses are expected to reveal novel mechanistic details for macromolecular protein dynamics. To ensure that any observed conformational change is physiologically relevant and not constrained by 3D crystal packing, it would be preferable for experiments to utilize small protein samples such as single particles or 2D crystals that mimic the target protein's native environment. These samples are not typically amenable to X-ray analysis, but transmission electron microscopy has imaged such sample geometries for over 40 years using both direct imaging and diffraction modes. While conventional transmission electron microscopes (TEM) have visualized biological samples with atomic resolution in an arrested or frozen state, the recent development of the dynamic TEM (DTEM) extends electron microscopy into a dynamic regime using pump-probe imaging. A new second-generation DTEM, which is currently being constructed, has the potential to observe live biological processes with unprecedented spatiotemporal resolution by using pulsed electron packets to probe the sample on micro- and nanosecond timescales. This article reviews the experimental parameters necessary for coupling DTEM with in situ liquid microscopy to enable direct imaging of protein conformational dynamics in a fully hydrated environment and visualize reactions propagating in real time. PMID:23315566

  15. Sintering Characteristics of Indian Chrome Ore Fines

    NASA Astrophysics Data System (ADS)

    Nandy, Bikash; Chaudhury, Manoj Kumar; Paul, Jagannath; Bhattacharjee, D.

    2009-10-01

    Chrome ore concentrate consists of high-temperature melting oxides such as Cr2O3, MgO, and Al2O3. The presence of these refractory constituents makes the ore a very high melting mineral. Hence, it is difficult to produce sinter from chrome ore by a pyrometallurgical route. Currently, chrome ore is ground to below 75 μm, pelletized, heat hardened through carbothermic reaction at 1300 °C to 1400 °C, and then charged into a submerged electric arc furnace (EAF), along with lumpy ore for ferrochrome/charge-chrome production. Electricity is a major cost element in this extraction process. This work explores the sinterability of chrome ore. The objective of this study was to: (1) determine whether chrome ore is sinterable and, if so, (2) ascertain ways of achieving satisfactory properties at a low temperature of sintering. Sintering of the raw material feed could be a way to reduce electricity consumption, because during sintering a partial reduction of minerals is expected along with agglomeration. Studies carried out by the authors show that it is possible to agglomerate chrome ore fines through sintering. The chrome ore sinter thus produced was found to be inferior in strength, comparable to that of an iron ore sinter, but strength requirements may not be the same for both. Because the heat generation during chrome ore sintering is high owing to some exothermic reactions, compared with iron ore, and because chrome ore contains a high amount of fines, shallow-bed-depth sinter cake production was attempted in the laboratory-scale pot-sintering machine. The sintered product was found to be a good conductor of electricity because of the presence of phases such as magnetite and maghemite. This characteristic of the chrome ore sinter will subsequently have a favorable impact in terms of power consumption during the production of ferrochrome in a submerged EAF. The sinter made was melted in the arc furnace and it was found that the specific melting energy is comparable to

  16. Faster rates with less catalyst in template-directed reactions

    NASA Technical Reports Server (NTRS)

    Kanavarioti, A.; Baird, E. E.

    1995-01-01

    We have recently shown that the polycytidylic acid-directed polymerization of guanosine 5'-monophosphate 2-methylimidazolide (2-MeImpG) is amenable to kinetic study and that rate determinations as a function of 2-MeImpG concentration can reveal much mechanistic detail (Kanavarioti et al. 1993). Here we report kinetic data which show that, once the reaction has been initiated by the formation of dimers, the elongation of dimers to form longer oligomers is accelerated by decreasing polycytidylate (poly(C)) concentration from 0.05 to 0.002 M. This result is consistent with the previously proposed mechanism. The increase in the observed pseudo-first order rate constant for formation of the trimer, k3', and the corresponding constant for formation of oligomers longer than the trimer, ki' (ki' is independent of oligomer length for i > or = 4), with decreasing template concentration for a given monomer concentration is attributed to an increase in template occupancy as template concentration is reduced.

  17. Nickel-Catalyzed Reactions Directed toward the Formation of Heterocycles.

    PubMed

    Kurahashi, Takuya; Matsubara, Seijiro

    2015-06-16

    Heterocycles have garnered significant attention because they are important functional building blocks in various useful molecules, such as pharmaceuticals, agricultural chemicals, pesticides, and materials. Several studies have been conducted regarding the preparation of heterocyclic skeletons with an emphasis on selectivity and efficiency. Three strategies are typically employed to construct cyclic molecules, namely, cyclization, cycloaddition, and ring-size alterations. Although each method has certain advantages, cycloaddition may be superior from the viewpoint of divergence. Specifically, cycloadditions enable the construction of rings from several pieces. However, the construction of heterocycles via cycloadditions is more challenging than the construction of carbocycles. For heterocycle construction, simple pericyclic reactions rarely work smoothly because of the large HOMO-LUMO gap unless well-designed combinations, such as electron-rich dienes and aldehydes, are utilized. Thus, a different approach should be employed to prepare heterocycles via cycloadditions. To this end, the use of metallacycles containing heteroatoms is expected to serve as a promising solution. In this study, we focused on the preparation of heteroatom-containing nickelacycles. Because nickel possesses a relatively high redox potential and an affinity for heteroatoms, several methods were developed to synthesize heteronickelacycles from various starting materials. The prepared nickelacycles were demonstrated to be reasonable intermediates in cycloaddition reactions, which were used to prepare various heterocycles. In this Account, we introduce the following four methods to prepare heterocycles via heteronickelacycles. (1) Direct oxidative insertion of Ni(0) to α,β-unsaturated enone derivatives: treatment of 3-ethoxycarbonyl-4-phenyl-3-buten-2-one with Ni(0) afforded an oxa-nickelacycle, which reacted with alkynes to give pyrans. (2) Substitution of a part of a cyclic compound with

  18. Effect of Annealing Treatments on the Microstructure, Mechanical Properties and Corrosion Behavior of Direct Metal Laser Sintered Ti-6Al-4V

    NASA Astrophysics Data System (ADS)

    Xu, Yangzi; Lu, Yuan; Sundberg, Kristin L.; Liang, Jianyu; Sisson, Richard D.

    2017-05-01

    An experimental investigation on the effects of post-annealing treatments on the microstructure, mechanical properties and corrosion behavior of direct metal laser sintered Ti-6Al-4V alloys has been conducted. The microstructure and phase evolution as affected by annealing treatment temperature were examined through scanning electron microscopy and x-ray diffraction. The tensile properties and Vickers hardness were measured and compared to the commercial Grade 5 Ti-6Al-4V alloy. Corrosion behavior of the parts was analyzed electrochemically in simulated body fluid at 37 °C. It was found out that the as-printed parts mainly composed of non-equilibrium α' phase. Annealing treatment allowed the transformation from α' to α phase and the development of β phase. The tensile test results indicated that post-annealing treatment could improve the ductility and decrease the strength. The as-printed Ti-6Al-4V part exhibits inferior corrosion resistance compared to the commercial alloy, and post-annealing treatment can reduce its susceptibility to corrosion by reducing the two-phase interface area.

  19. Tribological Behavior of Aluminum Alloy AlSi10Mg-TiB2 Composites Produced by Direct Metal Laser Sintering (DMLS)

    NASA Astrophysics Data System (ADS)

    Lorusso, Massimo; Aversa, Alberta; Manfredi, Diego; Calignano, Flaviana; Ambrosio, Elisa Paola; Ugues, Daniele; Pavese, Matteo

    2016-08-01

    Direct metal laser sintering (DMLS) is an additive manufacturing technique for the production of parts with complex geometry and it is especially appropriate for structural applications in aircraft and automotive industries. Aluminum-based metal matrix composites (MMCs) are promising materials for these applications because they are lightweight, ductile, and have a good strength-to-weight ratio This paper presents an investigation of microstructure, hardness, and tribological properties of AlSi10Mg alloy and AlSi10Mg alloy/TiB2 composites prepared by DMLS. MMCs were realized with two different compositions: 10% wt. of microsize TiB2, 1% wt. of nanosize TiB2. Wear tests were performed using a pin-on-disk apparatus on the prepared samples. Performances of AlSi10Mg samples manufactured by DMLS were also compared with the results obtained on AlSi10Mg alloy samples made by casting. It was found that the composites displayed a lower coefficient of friction (COF), but in the case of microsize TiB2 reinforcement the wear rate was higher than with nanosize reinforcements and aluminum alloy without reinforcement. AlSi10Mg obtained by DMLS showed a higher COF than AlSi10Mg obtained by casting, but the wear rate was higher in the latter case.

  20. Fundamental studies of retrograde reactions in direct liquefaction

    SciTech Connect

    Serio, M.A.; Solomon, P.R.; Kroo, E.; Charpenay, S.; Bassilakis, R.

    1991-12-17

    The overall objective of the program was to improve the understanding of retrograde reactions and their dependencies on coal rank and structure, and/or coal modifications and reaction conditions. Because retrograde reactions are competitive with bond breaking reactions, an understanding of both is required to shift the competition in favor of the latter. Related objectives were to clarify the conflicting observations reported in literature on such major topics as the role of oxygen groups in retrograde reactions and to provide a bridge from very fundamental studies on pure compounds to phenomenological studies on actual coal. This information was integrated into the FG-DVC model, which was improved and extended to the liquefaction context.

  1. Die-attach for power devices using the Ag sintering process: Interfacial microstructure and mechanical strength

    NASA Astrophysics Data System (ADS)

    Lee, Byung-Suk; Yoon, Jeong-Won

    2017-09-01

    The sintering reactions and mechanical reliability of Ag sinter paste with three different surface finishes, Cu, Ag, and electroless nickel-immersion gold, were evaluated during the sintering process. We compare the sintering reaction behaviors of the three sintered joints and identify the relationship between the sintering behavior and the sintered Ag/substrate compatibility. Inter-diffusion behaviors result in of good metallurgical bonding during the Ag sintering process in the three sintered joints. The shear strength increases on increasing the bonding pressure, irrespective of the surface finish. The surface finish material of the substrate strongly affects the shear strength of the Ag sintered joints. The Ag finished joint exhibits superior interfacial stability and shear strength compared to the Cu and Au finished joints.

  2. Boron distribution in sintered silicon carbide

    SciTech Connect

    Carter, W.D.; Holloway, P.H. ); White, C.; Clausing, R. )

    1988-01-01

    Boron concentrations on intergranular and transgranular fracture areas in sintered SiC were measured; {alpha}-SiC grains oriented parallel to the fracture surface would fracture at the {alpha}-{beta} interphase boundary. Auger electron spectroscopy showed that boron does not segregate to these boundaries in sintered SiC. This conclusion was generalized to include the other types of SiC grain boundaries. The absence of boron at grain boundaries suggests that its role in sintering is not to enhance diffusion rates. Chemical reactions and free surface segregation, which may explain the increased densification of SiC when B is present, are discussed.

  3. Immediate, non-submerged, root-analogue direct laser metal sintering (DLMS) implants: a 1-year prospective study on 15 patients.

    PubMed

    Mangano, Francesco Guido; De Franco, Michele; Caprioglio, Alberto; Macchi, Aldo; Piattelli, Adriano; Mangano, Carlo

    2014-07-01

    This study evaluated the 1-year survival and success rate of root-analogue direct laser metal sintering (DLMS) implants, placed into the extraction sockets of 15 patients. DLMS is a technology which allows solids with complex geometry to be fabricated by annealing metal powder microparticles in a focused laser beam, according to a computer-generated three-dimensional (3D) model; the fabrication process involves the laser-induced fusion of titanium microparticles, in order to build, layer-by-layer, the desired object. Cone-beam computed tomography (CBCT) acquisition and 3D image conversion, combined with the DLMS process, allow the fabrication of custom-made, root-analogue implants (RAIs). CBCT images of 15 non-restorable premolars (eight maxilla; seven mandible) were acquired and transformed into 3D models: from these, custom-made, root-analogue DLMS implants with integral abutment were fabricated. Immediately after tooth extraction, the RAIs were placed in the sockets and restored with a single crown. One year after implant placement, clinical and radiographic parameters were assessed: success criteria included absence of pain, suppuration, and exudation; absence of implant mobility and absence of continuous peri-implant radiolucency; distance between the implant shoulder and the first visible bone-to-implant contact <1.5 mm from initial surgery; and absence of prosthetic complications. At the 1-year follow-up, no implants were lost, for a survival rate of 100 %. All implants were stable, with no signs of infection. The good conditions of the peri-implant tissues were confirmed by the radiographic examination, with a mean DIB of 0.7 mm (±0.2). The possibility of fabricating custom-made, RAI DLMS implants opens new interesting horizons for immediate placement of dental implants.

  4. Immediate loading of mandibular overdentures supported by one-piece, direct metal laser sintering mini-implants: a short-term prospective clinical study.

    PubMed

    Mangano, Francesco G; Caprioglio, Alberto; Levrini, Luca; Farronato, Davide; Zecca, Piero A; Mangano, Carlo

    2015-02-01

    Only a few studies have dealt with immediately loaded, unsplinted mini-implants supporting ball attachment-retained mandibular overdentures (ODs). The aim of this study is to evaluate treatment outcomes of ball attachment-retained mandibular ODs supported by one-piece, unsplinted, immediately loaded, direct metal laser sintering (DMLS) mini-implants. Over a 4-year period (2009 to 2012), all patients referred to the Dental Clinic, University of Varese, and to a private practice for treatment with mandibular ODs were considered for inclusion in this study. Each patient received three or four DMLS mini-implants. Immediately after implant placement, a mandibular OD was connected to the implants. At each annual follow-up session, clinical and radiographic parameters were assessed, including the following outcome measures: 1) implant failures; 2) peri-implant marginal bone loss; and 3) complications. Statistical analysis was conducted using a life-table analysis. A total of 231 one-piece DMLS mini-implants were inserted in 62 patients. After 4 years of loading, six implants failed, giving an overall cumulative survival rate of 96.9%. The mean distance between the implant shoulder and the first visible bone-to-implant contact was 0.38 ± 0.25 and 0.62 ± 0.20 mm at the 1- and 4-year follow-up examinations, respectively. An incidence of 6.0% of biologic complications was reported; prosthetic complications were more frequent (12.9%). Within the limits of this study, it can be concluded that the immediate loading of one-piece, unsplinted, DMLS titanium mini-implants by means of ball attachment-supported mandibular ODs is a successful treatment procedure. Long-term follow-up studies are needed to confirm these results.

  5. Chemical Reaction Engineering: Current Status and Future Directions.

    ERIC Educational Resources Information Center

    Dudukovic, M. P.

    1987-01-01

    Describes Chemical Reaction Engineering (CRE) as the discipline that quantifies the interplay of transport phenomena and kinetics in relating reactor performance to operating conditions and input variables. Addresses the current status of CRE in both academic and industrial settings and outlines future trends. (TW)

  6. Direct Measurement of {sup 21}Na+{alpha} Stellar Reaction

    SciTech Connect

    Binh, D. N.; Kubono, S.; Yamaguchi, H.; Hayakawa, S.; Hashimoto, T.; Kahl, D.; Teranishi, T.; Iwasa, N.; Kume, N.; Kato, S.; Khiem, L. H.; Tho, N. T.; Wakabayashi, Y.

    2010-08-12

    The measurement of the resonant alpha scattering and the {sup 21}Na({alpha}, p) reaction were performed for the first time in inverse kinematics with the thick target method using a {sup 21}Na radioisotope (RI) beam. This paper reports the current result of alpha scattering measurement and its astrophysics implication.

  7. Chemical Reaction Engineering: Current Status and Future Directions.

    ERIC Educational Resources Information Center

    Dudukovic, M. P.

    1987-01-01

    Describes Chemical Reaction Engineering (CRE) as the discipline that quantifies the interplay of transport phenomena and kinetics in relating reactor performance to operating conditions and input variables. Addresses the current status of CRE in both academic and industrial settings and outlines future trends. (TW)

  8. Recent Results of Direct Nuclear Reaction Experiments for Stellar Nucleosynthesis

    NASA Astrophysics Data System (ADS)

    Cherubini, Silvio

    Nuclear cross sections between charged particles at stellar energies are among the faintest to be measured in nuclear physics. In order to overcome the experimental problems connected to these measurements, indirect methods where proposed and used in many experiments over the last decades. One of these, the Trojan Horse method, is based on the Quasi-Free reaction mechanism and proved to be particularly flexible and reliable and it allowed for the measurement of the cross sections of various reactions of astrophysical interest. The use and reliability of indirect methods become even more important when reactions induced by Radioactive Ion Beams are considered. As an example we will report here on the first measurement of 18F(p, α)15O process in Nova conditions by applying the Trojan Horse method to the 18F(d, α 15O)n reaction. In order to establish the reliability of such an approach, the Treiman-Yang criterion is an important test and it will also be addressed in this paper.

  9. Probing the Tetrahymena group I ribozyme reaction in both directions.

    PubMed

    Karbstein, Katrin; Carroll, Kate S; Herschlag, Daniel

    2002-09-17

    The Tetrahymena L-21 ScaI ribozyme derived from the self-splicing group I intron catalyzes a reversible reaction analogous to the first step of self-splicing: CCCUCUA (S) + [UC]G right harpoon over left harpoon CCCUCU (P) + [UC]GA. To relate our understanding of the ribozyme to the self-splicing reaction and to further the mechanistic dissection of the ribozyme reaction, we have established a quantitative kinetic and thermodynamic framework for the forward and reverse reaction of the L-21 ScaI ribozyme under identical conditions. Examination of the framework shows that binding of products is cooperative with binding enhanced 5-fold, as was observed previously for binding of the substrates. Further, binding of UCGA is 12-fold weaker than binding of the unphosphorylated UCG, analogous to the 20-fold weaker binding of phosphorylated S relative to P; the molecular interactions underlying the stronger binding of UCG were traced to the 3'-hydroxyl group of UCG. The symmetrical effects on binding of substrates and products result in the equilibrium between ribozyme-bound species, K(int), that is essentially unperturbed from the solution equilibrium, K(ext) (K(int) = [E.P.UCGA]/[E.S.UCG] = 4.6 and K(ext) = [P][UCGA]/[S][UCG] = 1.9). Last, we show that the pK(a) values of the nucleophiles in the forward and reverse reactions are >/=10. This observation suggests that metal ion activation of the nucleophile and stabilization of the leaving group can only account for a portion of the rate enhancement of this ribozyme. These and prior results suggest that the Tetrahymena group I ribozyme, analogous to protein enzymes, uses multiple catalytic strategies to achieve its large rate enhancement.

  10. Direct reaction measurements with a (132)Sn radioactive ion beam

    SciTech Connect

    Jones, K. L.; Chae, K. Y.; Kapler, R.; Ma, Zhanwen; Moazen, Brian; Cizewski, J. A.; Hatarik, Robert; Pain, S. D.; Swan, T. P.; Nunes, F. M.; Adekola, Aderemi S; Bardayan, Daniel W; Blackmon, Jeff C; Chae, Kyung Yuk; Liang, J Felix; Nesaraja, Caroline D; Pain, Steven D; Shapira, Dan; Smith, Michael Scott; Chipps, Kelly A; Erikson, Luke; Livesay, R. J.; Harlin, Christopher W; Patterson, N. P.; Thomas, J. S.; Kozub, R. L.; Shriner, Jr., John F

    2011-01-01

    The (d,p) neutron transfer and (d,d) elastic scattering reactions were measured in inverse kinematics using a radioactive ion beam of {sup 132}Sn at 630 MeV. The elastic scattering data were taken in a region where Rutherford scattering dominated the reaction, and nuclear effects account for less than 8% of the elastic scattering cross section. The magnitude of the nuclear effects, in the angular range studied, was found to be independent of the optical potential used, allowing the transfer data to be normalized in a reliable manner. The neutron-transfer reaction populated a previously unmeasured state at 1363 keV, which is most likely the single-particle 3p{sub 1/2} state expected above the N=82 shell closure. The data were analyzed using finite-range adiabatic-wave calculations and the results compared with the previous analysis using the distorted-wave Born approximation. Angular distributions for the ground and first-excited states are consistent with the previous tentative spin and parity assignments. Spectroscopic factors extracted from the differential cross sections are similar to those found for the one-neutron states beyond the benchmark doubly magic nucleus {sup 208}Pb.

  11. Direct reaction measurements with a 132Sn radioactive ion beam

    SciTech Connect

    Jones, Katherine L.; Nunes, Filomena M.; Adekola, Aderemi S.; Bardayan, Dan W.; Blackmon, Jeff; Chae, K. Y.; Chipps, Kelly A.; Cizewski, Jolie A.; Erikson, Luke E.; Harlin, C.; Hatarik, R.; Kapler, R.; Kozub, Raymond L.; Liang, J. F.; Livesay, Ronald J.; Ma, Zhongguo J.; Moazen, B. H.; Nesaraja, Caroline D.; Pain, Steven D.; Patterson, N. P.; Shapira, Dan; Shriner, Jr., John F.; Smith, Michael S.; Swan, Thomas P.; Thomas, Jeff S.

    2011-09-01

    The (d,p) neutron transfer and (d,d) elastic scattering reactions were measured in inverse kinematics using a radioactive ion beam of 132Sn at 630 MeV. The elastic scattering data were taken in a region where Rutherford scattering dominated the reaction, and nuclear effects account for less than 8% of the elastic scattering cross section. The magnitude of the nuclear effects, in the angular range studied, was found to be independent of the optical potential used, allowing the transfer data to be normalized in a reliable manner. The neutron-transfer reaction populated a previously unmeasured state at 1363 keV, which is most likely the single-particle 3p1/2 state expected above the N = 82 shell closure. The data were analyzed using finite-range adiabatic-wave calculations and the results compared with the previous analysis using the distorted-wave Born approximation. Angular distributions for the ground and first-excited states are consistent with the previous tentative spin and parity assignments. Spectroscopic factors extracted from the differential cross sections are similar to those found for the one-neutron states beyond the benchmark doubly magic nucleus 208Pb.

  12. Behavior of New Zealand Ironsand During Iron Ore Sintering

    NASA Astrophysics Data System (ADS)

    Wang, Zhe; Pinson, David; Chew, Sheng; Rogers, Harold; Monaghan, Brian J.; Pownceby, Mark I.; Webster, Nathan A. S.; Zhang, Guangqing

    2016-02-01

    A New Zealand ironsand sample was characterized by scanning electron microscopy (SEM), X-ray fluorescence spectroscopy, qualitative and quantitative X-ray diffraction, and electron probe microanalysis. The titanomagnetite-rich ironsand was added into an industrial sinter blend in the proportion of 5 wt pct, and the mixture was uniaxially pressed into cylindrical tablets and sintered in a tube furnace under flowing gas with various oxygen potentials and temperatures to develop knowledge and understanding of the behavior of titanium during sintering. An industrial sinter with the addition of 3 wt pct ironsand was also examined. Both the laboratory and industrial sinters were characterized by optical and SEM. Various morphologies of relict ironsand particles were present in the industrial sinter due to the heterogeneity of sintering conditions, which could be well simulated by the bench-scale sintering experiments. The assimilation of ironsand during sintering in a reducing atmosphere started with the diffusion of calcium into the lattice of the ironsand matrix, and a reaction zone was formed near the boundary within individual ironsand particles where a perovskite phase was generated. With increasing sintering temperature, in a reducing atmosphere, ironsand particles underwent further assimilation and most of the titanium moved from the ironsand particles into a glass phase. In comparison, more titanium remained in the original ironsand particles when sintered in air. Ironsand particles are more resistant to assimilation in an oxidizing atmosphere.

  13. Sintered plaque characteristics

    NASA Technical Reports Server (NTRS)

    Vaidyanathan, H.

    1982-01-01

    The structural transformations occurring during sintering, the fabrication of a slurry produced sintered plaque, are detailed. Degradation of the positive electrode in performance in cycling in a nickel hydrogen battery were traced to the quality of the sintered plaque. Electrode degradation was found to be a limiting factor in the battery cycle life. Details of microstructural characterization and distribution of pores, examination of plastic flow during shrinkage, and observations of the rounding of nickel powder particles during the slurry process are presented.

  14. Sintered plaque characteristics

    NASA Astrophysics Data System (ADS)

    Vaidyanathan, H.

    1982-03-01

    The structural transformations occurring during sintering, the fabrication of a slurry produced sintered plaque, are detailed. Degradation of the positive electrode in performance in cycling in a nickel hydrogen battery were traced to the quality of the sintered plaque. Electrode degradation was found to be a limiting factor in the battery cycle life. Details of microstructural characterization and distribution of pores, examination of plastic flow during shrinkage, and observations of the rounding of nickel powder particles during the slurry process are presented.

  15. Methods of flash sintering

    DOEpatents

    Raj, Rishi; Cologna, Marco; Francis, John S.

    2016-05-10

    This disclosure provides methods of flash sintering and compositions created by these methods. Methods for sintering multilayered bodies are provided in which a sintered body is produced in less than one minute. In one aspect, each layer is of a different composition, and may be constituted wholly from a ceramic or from a combination of ceramic and metallic particles. When the body includes a layer of an anode composition, a layer of an electrolyte composition and a layer of a cathode composition, the sintered body can be used to produce a solid oxide fuel cell.

  16. DIRECT MEASUREMENT OF MERCURY REACTIONS IN COAL POWER PLANT PLUMES

    SciTech Connect

    Leonard Levin

    2006-06-01

    This project was awarded under U.S. Department of Energy (DOE) National Energy Technology Laboratory (NETL) Program Solicitation DE-PS26-02NT41422 and specifically addresses Program Area of Interest: No.5--Environmental and Water Resources. The project team includes the Electric Power Research Institute (EPRI) as the contractor and the University of North Dakota Energy & Environmental Research Center (EERC) and Frontier Geosciences as subcontractors. Wisconsin Energies and its Pleasant Prairie Power Plant acted as host for the field-testing portion of the research. The project is aimed at clarifying the role, rates, and end results of chemical transformations that may occur to mercury that has been emitted from elevated stacks of coal-fired electric power plants. Mercury emitted from power plants emerges in either its elemental, divalent, or particulate-bound form. Deposition of the divalent form is more likely to occur closer to the source than that of the other two forms, due to its solubility in water. Thus, if chemical transformations occur in the stack emissions plume, measurements in the stack may mischaracterize the fate of the material. Initial field and pilot plant measurements have shown significant and rapid chemical reduction of divalent to elemental mercury may occur in these plumes. Mercury models currently assume that the chemical form of mercury occurring in stacks is the same as that which enters the free atmosphere, with no alteration occurring in the emissions plume. Recent data indicate otherwise, but need to be evaluated at full operating scale under field conditions. Prestbo and others have demonstrated the likelihood of significant mercury chemical reactions occurring in power plant plumes (Prestbo et al., 1999; MDNR-PPRP, 2000; EERC, 2001). This experiment will thus increase our understanding of mercury atmospheric chemistry, allowing informed decisions regarding source attribution. The experiment was carried out during the period August 22

  17. DIRECT MEASUREMENT OF MERCURY REACTIONS IN COAL POWER PLANT PLUMES

    SciTech Connect

    Leonard Levin

    2004-01-01

    This project was awarded under U.S. Department of Energy (DOE) National Energy Technology Laboratory (NETL) Program Solicitation DE-PS26-02NT41422 and specifically addresses Program Area of Interest: No.5--Environmental and Water Resources. The project team includes the Electric Power Research Institute (EPRI) as the contractor and the University of North Dakota Energy & Environmental Research Center (EERC) and Frontier Geosciences as subcontractors. Wisconsin Energies and its Pleasant Prairie Power Plant acted as host for the field-testing portion of the research. The project is aimed at clarifying the role, rates, and end results of chemical transformations that may occur to mercury that has been emitted from elevated stacks of coal-fired electric power plants. Mercury emitted from power plants emerges in either its elemental, divalent, or particulate-bound form. Deposition of the divalent form is more likely to occur closer to the source than that of the other two forms, due to its solubility in water. Thus, if chemical transformations occur in the stack emissions plume, measurements in the stack may mischaracterize the fate of the material. Initial field and pilot plant measurements have shown significant and rapid chemical reduction of divalent to elemental mercury may occur in these plumes. Mercury models currently assume that the chemical form of mercury occurring in stacks is the same as that which enters the free atmosphere, with no alteration occurring in the emissions plume. Recent data indicate otherwise, but need to be evaluated at full operating scale under field conditions. Prestbo and others have demonstrated the likelihood of significant mercury chemical reactions occurring in power plant plumes (Prestbo et al., 1999; MDNR-PPRP, 2000; EERC, 2001). This experiment will thus increase our understanding of mercury atmospheric chemistry, allowing informed decisions regarding source attribution. The experiment was carried out during the period August 22

  18. Criegee Intermediates: What Direct Production and Detection Can Teach Us About Reactions of Carbonyl Oxides

    NASA Astrophysics Data System (ADS)

    Taatjes, Craig A.

    2017-05-01

    The carbonyl oxide intermediates in the ozonolysis of alkenes, often known as Criegee intermediates, are potentially important reactants in Earth's atmosphere. For decades, careful analysis of ozonolysis systems was employed to derive an understanding of the formation and reactions of these species. Recently it has proved possible to synthesize at least some of these intermediates separately from ozonolysis, and hence to measure their reaction kinetics directly. Direct measurements have allowed new or more detailed understanding of each type of gas-phase reaction that carbonyl oxides undergo, often acting as a complement to highly detailed ozonolysis experiments. Moreover, the use of direct characterization methods to validate increasingly accurate theoretical investigations can enhance their impact well beyond the set of specific reactions that have been measured. Reactions that initiate particles or fuel their growth could be a new frontier for direct measurements of Criegee intermediate chemistry.

  19. Experimental Guidance of ISB Corrections via Direct Nuclear Reactions

    NASA Astrophysics Data System (ADS)

    Leach, K. G.; Garrett, P. E.; Ball, G. C.; Bangay, J. C.; Bianco, L.; Demand, G. A.; Faestermann, T.; Finlay, P.; Green, K. L.; Hertenberger, R.; Kriicken, R.; Phillips, A. A.; Rand, E. T.; Sumithrarachchi, C. S.; Svensson, C. E.; Towner, I. S.; Triambak, S.; Wirth, H.-F.; Wong, J.

    2011-09-01

    The most recent isospin-symmetry-breaking corrections, δc, of Towner and Hardy for superallowed Fermi β-decay transitions, have included the opening of specific core orbitals. This change has resulted in significant deviations in some of the δc factors from their previous calculations, and an improved agreement of the individual corrected Script Ft values with the overall world average of the 13 most precise cases. While this is consistent with the conserved-vector-current (CVC) hypothesis of the Standard Model, these new calculations must be thoroughly tested, and guidance must be given for the improvement of calculations for the upper-pf shell nuclei. Using the (d,t) reaction mechanism to probe the single neutron wavefunction overlap, information regarding the relevant shell-model configurations needed in the calculation can be determined. An experiment was therefore performed with a 22 MeV polarized deuterium beam from the MP tandem Van de Graaff accelerator in Munich, Germany. Using the Q3D magnetic spectrograph, and a cathode-strip focal-plane detector, outgoing tritons were analyzed at 9 angles between 10° and 60°, up to an excitation energy of 4.8 MeV. This proceeding reports the motivational and experimental details for the 64Zn(d,t)63Zn transfer work presented.

  20. Evaluation of sintering effects on SiC-incorporated UO2 kernels under Ar and Ar-4%H2 environments

    NASA Astrophysics Data System (ADS)

    Silva, Chinthaka M.; Lindemer, Terrence B.; Hunt, Rodney D.; Collins, Jack L.; Terrani, Kurt A.; Snead, Lance L.

    2013-11-01

    Silicon carbide (SiC) is suggested as an oxygen getter in UO2 kernels used for tristructural isotropic (TRISO) particle fuels and to prevent kernel migration during irradiation. Scanning electron microscopy and X-ray diffractometry analyses performed on sintered kernels verified that an internal gelation process can be used to incorporate SiC in UO2 fuel kernels. Even though the presence of UC in either argon (Ar) or Ar-4%H2 sintered samples suggested a lowering of the SiC up to 3.5-1.4 mol%, respectively, the presence of other silicon-related chemical phases indicates the preservation of silicon in the kernels during sintering process. UC formation was presumed to occur by two reactions. The first was by the reaction of SiC with its protective SiO2 oxide layer on SiC grains to produce volatile SiO and free carbon that subsequently reacted with UO2 to form UC. The second process was direct UO2 reaction with SiC grains to form SiO, CO, and UC. A slightly higher density and UC content were observed in the sample sintered in Ar-4%H2, but both atmospheres produced kernels with ˜95% of theoretical density. It is suggested that incorporating CO in the sintering gas could prevent UC formation and preserve the initial SiC content.

  1. Evaluation of fit of cement-retained implant-supported 3-unit structures fabricated with direct metal laser sintering and vacuum casting techniques.

    PubMed

    Oyagüe, Raquel Castillo; Sánchez-Turrión, Andrés; López-Lozano, José Francisco; Montero, Javier; Albaladejo, Alberto; Suárez-García, María Jesús

    2012-07-01

    This study evaluated the vertical discrepancy of implant-fixed 3-unit structures. Frameworks were constructed with laser-sintered Co-Cr, and vacuum-cast Co-Cr, Ni-Cr-Ti, and Pd-Au. Samples of each alloy group were randomly luted in standard fashion using resin-modified glass-ionomer, self-adhesive, and acrylic/urethane-based cements (n = 12 each). Discrepancies were SEM analyzed. Three-way ANOVA and Student-Newman-Keuls tests were run (P < 0.05). Laser-sintered structures achieved the best fit per cement tested. Within each alloy group, resin-modified glass-ionomer and acrylic/urethane-based cements produced comparably lower discrepancies than the self-adhesive agent. The abutment position did not yield significant differences. All misfit values could be considered clinically acceptable.

  2. Development of TiN particulates reinforced SS316 based metal matrix composite by direct metal laser sintering technique and its characterization

    NASA Astrophysics Data System (ADS)

    Hussain, Manowar; Mandal, Vijay; Kumar, Vikas; Das, A. K.; Ghosh, S. K.

    2017-12-01

    The present study describes the fabrication of TiN particulates reinforced SS316 based Metal Matrix Composites (MMCs) in nitrogen and argon atmosphere. The influence of sintering process parameters on microstructure, density, porosity, wear rate and microhardness of the fabricated samples has been analyzed. The input variable process parameters, such as, laser power density (range: 4.13-5.57 W/cm2 (× 104)), scanning speed (range: 3500-4500 mm/min) and the constant parameters, such as, laser beam diameter (0.4 mm), hatching distance (0.2 mm) and layer thickness (0.4 mm) have been considered in the process. It has been observed from Field Emission Scanning Electron Microscopy (FESEM) analysis that TiN and SS316 powder mixture can be sintered in which chromium acts as a binder. Fine gaps are not found at the interface between TiN and SS316 when the mixture is sintered in nitrogen atmosphere. With an increase in the percentage of TiN, the density and wear rate decreases. However, when the reinforcement is taken beyond 18% by weight, the wear rate starts increasing. The microhardness also increases with an increase in the percentage of TiN. The microstructure, elemental compositions and phase characterization of the developed sintered MMCs have been examined by FESEM, EDX (Energy-dispersive X-ray spectroscopy) and XRD (X-ray diffractometer) analysis, respectively. The results have demonstrated the suitability of the TiN reinforced SS316 MMCs for industrial applications.

  3. Quantitative Assignment of Reaction Directionality in a Multicompartmental Human Metabolic Reconstruction

    PubMed Central

    Haraldsdóttir, H.S.; Thiele, I.; Fleming, R.M.T.

    2012-01-01

    Reaction directionality is a key constraint in the modeling of genome-scale metabolic networks. We thermodynamically constrained reaction directionality in a multicompartmental genome-scale model of human metabolism, Recon 1, by calculating, in vivo, standard transformed reaction Gibbs energy as a function of compartment-specific pH, electrical potential, and ionic strength. We show that compartmental pH is an important determinant of thermodynamically determined reaction directionality. The effects of pH on transport reaction thermodynamics are only seen to their full extent when metabolites are represented as pseudoisomer groups of multiple protonated species. We accurately predict the irreversibility of 387 reactions, with detailed propagation of uncertainty in input data, and manually curate the literature to resolve conflicting directionality assignments. In at least half of all cases, a prediction of a reversible reaction directionality is due to the paucity of compartment-specific quantitative metabolomic data, with remaining cases due to uncertainty in estimation of standard reaction Gibbs energy. This study points to the pressing need for 1), quantitative metabolomic data, and 2), experimental measurement of thermochemical properties for human metabolites. PMID:22768925

  4. Microwave sintered nanocomposite electrodes for solid oxide fuel cells.

    PubMed

    Raza, Rizwan; Zhu, Bin

    2011-06-01

    Microwave sintering is a very interesting subject, which provides an alternative method to overcome problems faced with conventional sintering. This process is very efficient and only requires a few minutes. In this paper, nanocomposite electrodes (Cu0.15Ni0.85-GDC) were sintered at 700 degrees C for 10 mins in a single mode 2.45 GHz microwave oven by the solid state reaction method. The composition influence and the sintering methods on the as-obtained powder were characterized by XRD, SEM and TEM. It was observed that excellent sintering took place. Excellent fuel cell performance was achieved with microwave sintering compared tosamples sintered using conventional sintering. Electrochemical analysis was carried out using AC Impedance technique. This paper reports a new approach to develop a microwave sintered based nanocomposite material, which is more efficient on time and energy. This method can gain significant economical benefits compared to conventional sintered materials for applications in low temperature solid oxide fuel cells (LTSOFC).

  5. Direct simulation of electron transfer reactions in DNA radical cations

    PubMed Central

    Steinbrecher, Thomas; Koslowski, Thorsten; Case, David A.

    2009-01-01

    The electron transfer properties of DNA radical cations are important in DNA damage and repair processes. Fast long-range charge transfer has been demonstrated experimentally, but the subtle influences that experimental conditions as well as DNA sequences and geometries have on the details of electron transfer parameters are still poorly understood. In this work, we employ an atomistic QM/MM approach, based on a one-electron tight binding Hamiltonian and a classical molecular mechanics forcefield, to conduct nanosecond length MD simulations of electron holes in DNA oligomers. Multiple spontaneous electron transfer events were observed in 100 ns simulations with neighbouring adenine or guanine bases. Marcus parameters of charge transfer could be extracted directly from the simulations. The reorganisation energy λ for hopping between neighbouring bases was found to be ca. 25 kcal/mol and charge transfer rates of 4.1×109 s−1 for AA hopping and 1.3×109 s−1 for GG hopping were obtained. PMID:19049302

  6. Sintered wire cesium dispenser photocathode

    DOEpatents

    Montgomery, Eric J; Ives, R. Lawrence; Falce, Louis R

    2014-03-04

    A photoelectric cathode has a work function lowering material such as cesium placed into an enclosure which couples a thermal energy from a heater to the work function lowering material. The enclosure directs the work function lowering material in vapor form through a low diffusion layer, through a free space layer, and through a uniform porosity layer, one side of which also forms a photoelectric cathode surface. The low diffusion layer may be formed from sintered powdered metal, such as tungsten, and the uniform porosity layer may be formed from wires which are sintered together to form pores between the wires which are continuous from the a back surface to a front surface which is also the photoelectric surface.

  7. Enantioselective desymmetrization of prochiral cyclohexanone derivatives via the organocatalytic direct Aldol reaction.

    PubMed

    Jiang, Jun; He, Long; Luo, Shi-Wei; Cun, Lin-Feng; Gong, Liu-Zhu

    2007-02-21

    Asymmetric desymmetrization of 4-substituted cyclohexanones using proline amide-catalyzed direct aldol reaction afforded beta-hydroxyketones with three stereogenic centers in high enantioselectivities of up to >99% ee.

  8. Microstructural and continuum evolution modeling of sintering.

    SciTech Connect

    Braginsky, Michael V.; Olevsky, Eugene A.; Johnson, D. Lynn; Tikare, Veena; Garino, Terry J.; Arguello, Jose Guadalupe, Jr.

    2003-12-01

    deformation during. The continuum portion is based on a finite element formulation that allows 3D components to be modeled using SNL's nonlinear large-deformation finite element code, JAS3D. This tool provides a capability to model sintering of complex three-dimensional components. The model was verified by comparing to simulations results published in the literature. The model was validated using experimental results from various laboratory experiments performed by Garino. In addition, the mesoscale simulations were used to study anisotropic shrinkage in aligned, elongated powder compacts. Anisotropic shrinkage occurred in all compacts with aligned, elongated particles. However, the direction of higher shrinkage was in some cases along the direction of elongation and in other cases in the perpendicular direction depending on the details of the powder compact. In compacts of simple-packed, mono-sized, elongated particles, shrinkage was higher in the direction of elongation. In compacts of close-packed, mono-sized, elongated particles and of elongated particles with a size and shape distribution, the shrinkage was lower in the direction of elongation. We also explored the concept of a sintering stress tensor rather than the traditional sintering stress scalar concept for the case of anisotropic shrinkage. A thermodynamic treatment of this is presented. A method to calculate the sintering stress tensor is also presented. A user-friendly code that can simulate microstructural evolution during sintering in 2D and in 3D was developed. This code can run on most UNIX platforms and has a motif-based GUI. The microstructural evolution is shown as the code is running and many of the microstructural features, such as grain size, pore size, the average grain boundary length (in 2D) and area (in 3D), etc. are measured and recorded as a function of time. The overall density as the function of time is also recorded.

  9. Direct picosecond time resolution of unimolecular reactions initiated by local mode excitation

    NASA Technical Reports Server (NTRS)

    Scherer, N. F.; Doany, F. E.; Zewail, A. H.; Perry, J. W.

    1986-01-01

    Attention is given to the first results of direct, picosec measurements of the Delta-nu(OH) 5 local mode transition of H2O2. These time-resolved studies yield a direct measure of the unimolecular dissociation rate, and furnish a lower limit for the rate of energy redistribution from the OH stretch to the O-O reaction coordinate. The data thus determined may be used to ascertain the domain of validity for statistical unimolecular reaction rate theories.

  10. Sintering titanium powders

    SciTech Connect

    Gerdemann, Stephen J.; Alman, David E.

    2005-09-01

    Recently, there has been renewed interest in low-cost titanium. Near-net-shape powder metallurgy offers the potential of manufacturing titanium articles without costly and difficult forming and machining operations; hence, processing methods such as conventional press-and-sinter, powder forging and powder injection molding are of interest. The sintering behavior of a variety of commercial and experimental titanium powders was studied. Commercial powders were acquired that were produced different routes: (i) sponge fines from the primary titanium processing; (ii) via the hydride-dehydride process; and (iii) gas atomization. The influence of vacuum sintering time (0.5 to 32 hrs) and temperature (1200, 1275 or 1350°C) on the microstructure (porosity present) of cold pressed powders was studied. The results are discussed in terms of the difference in powder characteristics, with the aim of identify the characteristics required for full density via press-and-sinter processing. Near-net-shape tensile bars were consolidated via cold pressed and sintered. After sintering, a sub-set of the tensile bars was hot-isostatic pressed (HIPed). The microstructure and properties of the bars were compared in the sintered and HIPed conditions.

  11. Novel hydrophilic nanostructured microtexture on direct metal laser sintered Ti-6Al-4V surfaces enhances osteoblast response in vitro and osseointegration in a rabbit model.

    PubMed

    Hyzy, Sharon L; Cheng, Alice; Cohen, David J; Yatzkaier, Gustavo; Whitehead, Alexander J; Clohessy, Ryan M; Gittens, Rolando A; Boyan, Barbara D; Schwartz, Zvi

    2016-08-01

    The purpose of this study was to compare the biological effects in vivo of hierarchical surface roughness on laser sintered titanium-aluminum-vanadium (Ti-6Al-4V) implants to those of conventionally machined implants on osteoblast response in vitro and osseointegration. Laser sintered disks were fabricated to have micro-/nano-roughness and wettability. Control disks were computer numerical control (CNC) milled and then polished to be smooth (CNC-M). Laser sintered disks were polished smooth (LST-M), grit blasted (LST-B), or blasted and acid etched (LST-BE). LST-BE implants or implants manufactured by CNC milling and grit blasted (CNC-B) were implanted in the femurs of male New Zealand white rabbits. Most osteoblast differentiation markers and local factors were enhanced on rough LST-B and LST-BE surfaces in comparison to smooth CNC-M or LST-M surfaces for MG63 and normal human osteoblast cells. To determine if LST-BE implants were osteogenic in vivo, we compared them to implant surfaces used clinically. LST-BE implants had a unique surface with combined micro-/nano-roughness and higher wettability than conventional CNC-B implants. Histomorphometric analysis demonstrated a significant improvement in cortical bone-implant contact of LST-BE implants compared to CNC-B implants after 3 and 6 weeks. However, mechanical testing revealed no differences between implant pullout forces at those time points. LST surfaces enhanced osteoblast differentiation and production of local factors in vitro and improved the osseointegration process in vivo. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 2086-2098, 2016. © 2016 Wiley Periodicals, Inc.

  12. Direct laser metal sintering as a new approach to fabrication of an isoelastic functionally graded material for manufacture of porous titanium dental implants.

    PubMed

    Traini, T; Mangano, C; Sammons, R L; Mangano, F; Macchi, A; Piattelli, A

    2008-11-01

    This work focuses on a titanium alloy implants incorporating a gradient of porosity, from the inner core to the outer surface, obtained by laser sintering of metal powder. Surface appearance, microstructure, composition, mechanical properties and fractography were evaluated. All the specimens were prepared by a selective laser sintering procedure using a Ti-6Al-4V alloy powder with a particle size of 1-10 microm. The morphological and chemical analyses were performed by SEM and energy dispersive X-ray spectroscopy. The flexure strength was determined by a three-point bend test using a universal testing machine. The surface roughness was investigated using a confocal scanning laser microscope. The surface roughness variation was statistically evaluated by use of a Chi square test. A p value of <0.05 was considered statistically significant. The original surface microstructure consisted of roughly spherical particles, diameter range 5-50 microm. After exposure to hydrofluoric acid some of these were removed and the microsphere diameter then ranged from 5.1 microm to 26.8 microm. Following an organic acid treatment, particles were replaced by grooves 14.6-152.5 microm in width and 21.4-102.4 microm depth. The metal core consisted of columnar beta grains with alpha and beta laths within the grains. The alloy was composed of 90.08% Ti, 5.67% Al and 4.25% V. The Young's modulus of the inner core material was 104+/-7.7 GPa; while that of the outer porous material was 77+/-3.5 GPa. The fracture face showed a dimpled appearance typical of ductile fracture. In conclusion, laser metal sintering proved to be an efficient means of construction of dental implants with a functionally graded material which is better adapted to the elastic properties of the bone. Such implants should minimize stress shielding effects and improve long-term performance.

  13. Direct catalytic asymmetric aldol reactions of thioamides: toward a stereocontrolled synthesis of 1,3-polyols.

    PubMed

    Iwata, Mitsutaka; Yazaki, Ryo; Suzuki, Yuta; Kumagai, Naoya; Shibasaki, Masakatsu

    2009-12-30

    A direct catalytic asymmetric aldol reaction of thioamides with a soft Lewis acid/hard Brønsted base cooperative catalytic system comprising (R,R)-Ph-BPE/[Cu(CH(3)CN)(4)]PF(6)/LiOAr is described. Highly chemoselective deprotonative activation of thioamides allows for a direct aldol reaction of alpha-nonbranched aliphatic aldehydes, which are susceptible to self-condensation. Facile reduction of the thioamide functionality and a catalyst-controlled second aldol reaction provides 1,3-diols in a highly stereoselective manner.

  14. Microwave sintering of ceramics

    SciTech Connect

    Snyder, W.B.

    1989-01-01

    Successful adaptation of microwave heating to the densification of ceramic materials require a marriage of microwave and materials technologies. Using an interdisciplinary team of microwave and materials engineers, we have successfully demonstrated the ability to density ceramic materials over a wide range of temperatures. Microstructural evolution during microwave sintering has been found to be significantly different from that observed in conventional sintering. Our results and those of others indicate that microwave sintering has the potential to fabricate components to near net shape with mechanical properties equivalent to hot pressed or hot isostatically pressed material. 6 refs., 11 figs.

  15. Sintered superhard materials.

    PubMed

    Wentorf, R H; Devries, R C; Bundy, F P

    1980-05-23

    Diamond or cubic boron nitride particles can be sintered into strong masses at high temperatures and very high pressures at which these crystalline forms are stable. Most of the desirable physical properties of the sintered masses, such as hardness and thermal conductivity, approach those of large single crystals; their resistance to wear and catastrophic splitting is superior. The sintered masses are produced on a commercial scale and are increasingly used as cutting tools on hard or abrasive materials, as wire-drawing dies, in rock drills, and in special high-pressure apparatus.

  16. Sintered superhard materials

    SciTech Connect

    Wentorf, R.H.; DeVries, R.C.; Bundy, F.P.

    1980-01-01

    Diamond of cubic boron nitride particles can be sintered into strong masses at high temperatures and very high pressures at which these crystalline forms are stable. Most of the desirable physical properties of the sintered masses, such as hardness and thermal conductivity, approach those of large single crystals; their resistance to wear and catastrophic splitting is superior. The sintered masses are produced on a commercial scale and are increasingly used as cutting tools on hard or abrasive materials, as wire-drawing dies, in rock drills, and in special high-pressure apparatus.

  17. Sintered Superhard Materials

    NASA Astrophysics Data System (ADS)

    Wentorf, R. H.; Devries, R. C.; Bundy, F. P.

    1980-05-01

    Diamond or cubic boron nitride particles can be sintered into strong masses at high temperatures and very high pressures at which these crystalline forms are stable. Most of the desirable physical properties of the sintered masses, such as hardness and thermal conductivity, approach those of large single crystals; their resistance to wear and catastrophic splitting is superior. The sintered masses are produced on a commercial scale and are increasingly used as cutting tools on hard or abrasive materials, as wire-drawing dies, in rock drills, and in special high-pressure apparatus.

  18. SINTERED REFRACTORY MASS

    DOEpatents

    Williams, A.E.

    1955-09-01

    A method is given for joining sintered masses of refractory compounds. It consists in maintaining the masses in contact with each other by application of a moderate pressure, while they are at sintering temperature. The sintered masses are subjected to am applied pressure of about 1/2 to 1 ton per square inch of the surface in contact for about 10 minutes, and the temperature employed may be fropn about 1400 deg C to 2000 deg C. Refractory oxides to which the invention may be applied are beryllia, alumina, thoria, and magnesia.

  19. Microwave sintering of ceramic materials

    NASA Astrophysics Data System (ADS)

    Karayannis, V. G.

    2016-11-01

    In the present study, the potential of microwave irradiation as an innovative energy- efficient alternative to conventional heating technologies in ceramic manufacturing is reviewed, addressing the advantages/disadvantages, while also commenting on future applications of possible commercial interest. Ceramic materials have been extensively studied and used due to several advantages they exhibit. Sintering ceramics using microwave radiation, a novel technology widely employed in various fields, can be an efficient, economic and environmentally-friendlier approach, to improve the consolidation efficiency and reduce the processing cycle-time, in order to attain substantial energy and cost savings. Microwave sintering provides efficient internal heating, as energy is supplied directly and penetrates the material. Since energy transfer occurs at a molecular level, heat is generated throughout the material, thus avoiding significant temperature gradients between the surface and the interior, which are frequently encountered at high heating rates upon conventional sintering. Thus, rapid, volumetric and uniform heating of various raw materials and secondary resources for ceramic production is possible, with limited grain coarsening, leading to accelerated densification, and uniform and fine-grained microstructures, with enhanced mechanical performance. This is particularly important for manufacturing large-size ceramic products of quality, and also for specialty ceramic materials such as bioceramics and electroceramics. Critical parameters for the process optimization, including the electromagnetic field distribution, microwave-material interaction, heat transfer mechanisms and material transformations, should be taken into consideration.

  20. Fundamental studies of retrograde reactions in direct liquefaction. Topical report, September 30, 1988--September 30, 1989

    SciTech Connect

    Serio, M.A.; Solomon, P.R.; Bassilakis, R.; Kroo, E.

    1989-12-31

    Most of the proposed processing schemes for improving liquefaction yields involve favoring bond-breaking and radical stabilization reactions over the retrograde reactions. The retrograde reactions are often encountered before liquefaction temperatures are reached. The objective of this program is to elucidate and model the retrograde reaction chemistry in direct coal liquefaction through the application of experimental techniques and theoretical models which have been successfully employed at Advanced Fuel Research (AFR) and SRI International (a subcontractor) to understand and predict coal reaction behavior. The study of retrograde reactions is being done using an integrated approach using extensive characterization of the liquefaction chemistry of three kinds of systems: (1) model polymers; (2) coal; and (3) modified coals.

  1. Sintering of model aerosol agglomerates

    SciTech Connect

    Lunden, M.M.; Flagan, R.C.

    1995-12-31

    Many processes form particles from vapor phase precursors, whereby particles nucleate and grow primarily by coagulation in the solid state. In some industries, such as those that produce fumed titania, silica, and carbon black, these particles are the desired end product. In other processes particle formation can be deleterious, such as the ashes produced by combustion processes which can foul heat transfer surfaces and be environmentally hazardous. Regardless of process, it is important to be able to understand and predict the structure of the particles being produced. The evolving particle population often only partially coalesces (or sinters) during coagulation, leading to agglomerate structures. Although the extent sintering during agglomeration has been described in a number of modeling studies and demonstrated qualitatively in several experimental investigations, no direct validation of those models has been reported. We report on controlled experimental investigations of the structural evolution of model agglomerate particles aimed at providing the necessary data base for such validation as well as a new modeling ideas designed to give a better physical understanding of the sintering process. Aggregate particle densification studies have been performed using mobility classified particles produced by low temperature, non-coalescent coagulation. Initial experiments were performed with small aggregates, primarily bispheres. The particles were thermally processed while still entrained in a carrier gas flow, and subsequently collected for electron microscope analysis of neck growth and other structural parameters. Larger aggregate particles, also produced by low temperature coagulation, have been similarly processed. Changes in the physical structure and aerodynamic drag of the particles have been examined. We have developed a model to describe the structural evolution of simple aggregates during sintering.

  2. Laser sintering of thick-film conductors for microelectronic applications

    NASA Astrophysics Data System (ADS)

    Kinzel, Edward C.; Sigmarsson, Hjalti H.; Xu, Xianfan; Chappell, William J.

    2007-03-01

    This paper investigates fabrication of functional thick metal films using simultaneous laser sintering and patterning along with the fundamental physical phenomena that govern the laser sintering process. The effects of the processing parameters on the quality of the fabricated components are investigated through a heat transfer analysis. We show that our process has potentials for metallization of microelectronics directly onto substrates whose melting temperatures are much lower than the temperature needed for sintering, which is only possible by properly controlling the temperature field during laser sintering. Optimum properties of the fabricated components are obtained when certain thermal conditions are produced during laser heating.

  3. Fabrication of 200 mm Diameter Sintering Body of Skutterudite Thermoelectric Material by Spark Plasma Sintering

    NASA Astrophysics Data System (ADS)

    Tomida, T.; Sumiyoshi, A.; Nie, G.; Ochi, T.; Suzuki, S.; Kikuchi, M.; Mukaiyama, K.; Guo, J. Q.

    2017-05-01

    Filled skutterudite is a promising material for thermoelectric power generation because its ZT value is relatively high. However, mass production of high-performance thermoelectric materials remains a challenge. This study focused on the sintering process of thermoelectric materials. Large-diameter n-type (Yb or La, Ca, Al, Ga, In)0.8(Co, Fe)4Sb12 skutterudite sintering bodies with a small thickness were successfully produced by the spark plasma sintering (SPS) method. When direct current flows through the thermoelectric sintering body during the SPS pulse, the Peltier effect causes a temperature difference within the sintering body. To eliminate the Peltier effect, an electrical insulating material was inserted between the punch (electrode) and the sintering body. In this way, an n-type La-filled skutterudite sample with a diameter of 200 mm, thickness of 21 mm, and weight of 5 kg was successfully produced. The thermoelectric properties and microstructures of the sample were almost the same throughout the whole sintering body, and the dimensionless figure of merit reached 1.0 at 773 K.

  4. Fabrication of 200 mm Diameter Sintering Body of Skutterudite Thermoelectric Material by Spark Plasma Sintering

    NASA Astrophysics Data System (ADS)

    Tomida, T.; Sumiyoshi, A.; Nie, G.; Ochi, T.; Suzuki, S.; Kikuchi, M.; Mukaiyama, K.; Guo, J. Q.

    2016-11-01

    Filled skutterudite is a promising material for thermoelectric power generation because its ZT value is relatively high. However, mass production of high-performance thermoelectric materials remains a challenge. This study focused on the sintering process of thermoelectric materials. Large-diameter n-type (Yb or La, Ca, Al, Ga, In)0.8(Co, Fe)4Sb12 skutterudite sintering bodies with a small thickness were successfully produced by the spark plasma sintering (SPS) method. When direct current flows through the thermoelectric sintering body during the SPS pulse, the Peltier effect causes a temperature difference within the sintering body. To eliminate the Peltier effect, an electrical insulating material was inserted between the punch (electrode) and the sintering body. In this way, an n-type La-filled skutterudite sample with a diameter of 200 mm, thickness of 21 mm, and weight of 5 kg was successfully produced. The thermoelectric properties and microstructures of the sample were almost the same throughout the whole sintering body, and the dimensionless figure of merit reached 1.0 at 773 K.

  5. Sintered wire annode

    DOEpatents

    Falce, Louis R.; Ives, R. Lawrence

    2007-12-25

    A plurality of high atomic number wires are sintered together to form a porous rod that is parted into porous disks which will be used as x-ray targets. A thermally conductive material is introduced into the pores of the rod, and when a stream of electrons impinges on the sintered wire target and generates x-rays, the heat generated by the impinging x-rays is removed by the thermally conductive material interspersed in the pores of the wires.

  6. Ferritin reactions: direct identification of the site for the diferric peroxide reaction intermediate.

    PubMed

    Liu, Xiaofeng; Theil, Elizabeth C

    2004-06-08

    Ferritins managing iron-oxygen biochemistry in animals, plants, and microorganisms belong to the diiron carboxylate protein family and concentrate iron as ferric oxide approximately 10(14) times above the ferric K(s). Ferritin iron (up to 4,500 atoms), used for iron cofactors and heme, or to trap DNA-damaging oxidants in microorganisms, is concentrated in the protein nanocage cavity (5-8 nm) formed during assembly of polypeptide subunits, 24 in maxiferritins and 12 in miniferritins/DNA protection during starvation proteins. Direct identification of ferritin ferroxidase (F(ox)) sites, complicated by multiple types of iron-ferritin interactions, is now achieved with chimeric proteins where putative F(ox) site residues were introduced singly and cumulatively into an inactive host, an L maxiferritin. A dimagnesium ferritin cocrystal model guided site design and the diferric peroxo F(ox) intermediates (A at 650 nm) monitored activity. Diferric peroxo formation in chimeric and WT proteins had similar K(app) values and Hill coefficients. Catalytic activity required cooperative ferrous substrate binding to two sites A (E, EXXH) and B (E, QXXD). The weaker B sites in ferritin contrast with stronger B sites (E, EXXH) in diiron carboxylate oxygenases, explaining diferric oxo/hydroxo product release in ferritin vs. diiron cofactor retention in oxygenases. Codons for Q/H and D/E differ by single nucleotides, suggesting simple DNA mutations relate site B diiron substrate sites and diiron cofactor sites in proteins. The smaller k(cat) values in chimeras indicate the absence of second-shell residues important for ferritin substrate-product channeling that, when identified, will outline the entire iron path from ferritin pores through the F(ox) site to the mineral cavity.

  7. Titanium processing using selective laser sintering

    NASA Astrophysics Data System (ADS)

    Harlan, Nicole Renee

    1999-11-01

    A materials development workstation specifically designed to test high temperature metal and metal-matrix composites for direct selective laser sintering (SLS) was constructed. Using the workstation, a titanium-aluminum alloy was sintered into single layer coupons to demonstrate the feasibility of producing titanium components using direct SLS. A combination of low temperature indirect SLS and colloidal infiltration was used to create "partially-stabilized" zirconia molds for titanium casting. The base material, stabilized zirconia mixed with a copolymer, was laser sintered into the desired mold geometry. The copolymer was pyrolyzed and replaced by a zirconia precursor. The flexural strength and surface roughness of the SLS-produced casting molds were sufficient for titanium casting trials. A laser-scanned human femur was used as the basis for a mold design and technology demonstration. Titanium castings produced from SLS molds exhibited typical as-cast microstructures and an average surface roughness (Ra) of 8 mum.

  8. Direct catalytic enantioselective vinylogous aldol reaction of α-branched enals with isatins.

    PubMed

    Cassani, Carlo; Melchiorre, Paolo

    2012-11-02

    The direct vinylogous aldol reaction of α-substituted α,β-unsaturated aldehydes with isatins is described. The chemistry provides easy access to valuable 3-substituted 3-hydroxyoxindole derivatives with high stereocontrol and perfect γ-site selectivity. Preliminary mechanistic studies suggest that, depending on the nature of the α-branched enal substituents, two divergent reaction mechanisms can be operating, leading to different products and stereochemical outcomes.

  9. Analysis of weblike network structures of directed graphs for chemical reactions in methane plasmas

    SciTech Connect

    Sakai, Osamu Nobuto, Kyosuke; Miyagi, Shigeyuki; Tachibana, Kunihide

    2015-10-15

    Chemical reactions of molecular gases like methane are so complicated that a chart of decomposed and/or synthesized species originating from molecules in plasma resembles a weblike network in which we write down species and reactions among them. Here we consider properties of the network structures of chemical reactions in methane plasmas. In the network, atoms/molecules/radical species are assumed to form nodes and chemical reactions correspond to directed edges in the terminology of graph theory. Investigation of the centrality index reveals importance of CH{sub 3} in the global chemical reaction, and difference of an index for each radical species between cases with and without electrons clarifies that the electrons are at an influential position to tighten the network structure.

  10. Modeling of chemical reactions between polyatomic molecules for atmospheric entry simulations with direct simulation Monte Carlo

    NASA Astrophysics Data System (ADS)

    Nizenkov, P.; Pfeiffer, M.; Mirza, A.; Fasoulas, S.

    2017-07-01

    For the simulation of atmospheric entry maneuvers at Mars and Saturn's Titan, the chemistry modeling of polyatomic molecules is implemented in the direct simulation Monte Carlo method within the reactive plasma flow solver PICLas. An additional reaction condition as well as the consideration of the vibrational degrees of freedom is described in the context of the total collision energy model. The treatment of reverse exchange and recombination reactions is discussed, where the low temperature exponent of the Arrhenius fit for methane dissociation limited the calculation of the reaction probability at relevant temperatures. An alternative method based on the equilibrium constant is devised. The post-reaction energy redistribution is performed under the assumption of equipartition of the remaining collisional energy. The implementation is verified for several reaction paths with simple reservoir simulations. Finally, the feasibility of the new chemistry model is demonstrated by a simulation of a trajectory point of Huygens probe at Titan.

  11. Catalytic asymmetric direct-type 1,4-addition reactions of simple amides.

    PubMed

    Suzuki, Hirotsugu; Sato, Io; Yamashita, Yasuhiro; Kobayashi, Shū

    2015-04-08

    The development of catalytic asymmetric direct-type reactions of less acidic carbonyl compounds such as amides and esters has been a challenging theme in organic chemistry for decades. Here we describe the asymmetric direct 1,4-addition reactions of simple amides with α,β-unsaturated carbonyl compounds using a catalytic amount of a novel chiral catalyst consisting of a potassium base and a macrocyclic chiral crown ether. The desired 1,5-dicarbonyl compounds were obtained in high yields with excellent diastereo- and enantioselectivities. This is the first example of a highly enantioselective catalytic direct-type reaction of simple amides. In addition, the structure of the chiral potassium catalyst has been investigated by X-ray crystallographic, dynamic (1)H NMR, and MALDI-TOF MS analyses.

  12. The Trojan Horse method for nuclear astrophysics: Recent results for direct reactions

    NASA Astrophysics Data System (ADS)

    Tumino, A.; Spitaleri, C.; Cherubini, S.; Gulino, M.; La Cognata, M.; Lamia, L.; Pizzone, R. G.; Rapisarda, G. G.; Romano, S.

    2014-05-01

    The Trojan Horse method is a powerful indirect technique to determine the astrophysical factor for binary rearrangement processes A+x→b+B at astrophysical energies by measuring the cross section for the Trojan Horse (TH) reaction A+a→B+b+s in quasi free kinematics. The Trojan Horse Method has been successfully applied to many reactions of astrophysical interest, both direct and resonant. In this paper, we will focus on direct sub-processes. The theory of the THM for direct binary reactions will be shortly presented based on a few-body approach that takes into account the off-energy-shell effects and initial and final state interactions. Examples of recent results will be presented to demonstrate how THM works experimentally.

  13. PRECO-D2: program for calculating preequilibrium and direct reaction double differential cross sections

    SciTech Connect

    Kalbach, C.

    1985-02-01

    The code PRECO-D2 uses the exciton model for preequilibrium nuclear reactions to describe the emission of particles with mass numbers of 1 to 4 from an equilibrating composite nucleus. A distinction is made between open and closed configurations in this system and between the multi-step direct (MSD) and multi-step compound (MSC) components of the preequilibrium cross section. Additional MSD components are calculated semi-empirically to account for direct nucleon transfer reactions and direct knockout processes involving cluster degrees of freedom. Evaporation from the equilibrated composite nucleus is included in the full MSC cross section. Output of energy differential and double differential cross sections is provided for the first particle emitted from the composite system. Multiple particle emission is not considered. This report describes the reaction models used in writing PRECO-D2 and explains the organization and utilization of the code. 21 refs.

  14. The Trojan Horse method for nuclear astrophysics: Recent results for direct reactions

    SciTech Connect

    Tumino, A.; Gulino, M.; Spitaleri, C.; Cherubini, S.; Romano, S.; Cognata, M. La; Pizzone, R. G.; Rapisarda, G. G.; Lamia, L.

    2014-05-09

    The Trojan Horse method is a powerful indirect technique to determine the astrophysical factor for binary rearrangement processes A+x→b+B at astrophysical energies by measuring the cross section for the Trojan Horse (TH) reaction A+a→B+b+s in quasi free kinematics. The Trojan Horse Method has been successfully applied to many reactions of astrophysical interest, both direct and resonant. In this paper, we will focus on direct sub-processes. The theory of the THM for direct binary reactions will be shortly presented based on a few-body approach that takes into account the off-energy-shell effects and initial and final state interactions. Examples of recent results will be presented to demonstrate how THM works experimentally.

  15. Direct Monte Carlo simulation of chemical reaction systems: Prediction of ultrafast detonations

    NASA Astrophysics Data System (ADS)

    Anderson, James B.; Long, Lyle N.

    2003-02-01

    Ultrafast detonations having steady-state velocities greater than predicted by the Chapman-Jouguet (C-J) and the Zeldovich-von Neumann-Döring (ZND) theories are predicted by direct simulations of detonation waves in gaseous reaction systems. The simulations are made using Bird's direct simulation Monte Carlo method which produces the full details of the coupled gas-dynamic and reaction effects as well as temperature, velocity, density, pressure, and species profiles for the detonation waves. The systems are simplified and clarified by restriction to one-dimensional flow with the reaction A+M→B+M having variable energy release and rate characteristics. For a slow reaction the reaction and shock regions are separated and the detonation wave proceeds at the forward speed of sound in the burned gas as predicted by the C-J and ZND theories. For a very fast reaction the reaction and shock waves overlap, the assumptions required for the C-J and ZND theories are no longer valid, the von Neumann spike is reduced, and the detonation velocity exceeds that predicted by the C-J and ZND theories to produce an ultrafast detonation.

  16. Microstructural changes on the reduction of imperial smelting furnace sinters

    NASA Astrophysics Data System (ADS)

    Lee, F. T.; Hayes, P. C.

    1993-02-01

    The reduction reactions of Imperial Smelting Furnace (ISF) sinter microstructure were investigated in simulated zinc blast furnace conditions. Initial and partially reduced samples were examined using optical, electron-probe microanalysis, scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX), and X-ray diffraction (XRD) to characterize the struc-tural and compositional changes occurring during the reduction reaction. The reaction mecha-nisms and reduction sequences for the various oxide phases within the sinter structure during reduction of ISF sinters under the system studied are discussed. The reduction of sinters resulted in the structural modification of zincite, franklinite, slag phases, and the formation of new oxide and metallic phases. The rate and sequence of these complex phase transformations were found to be dependent upon reduction time, temperature, and the reacting gas composition.

  17. Noncovalent Substrate-Directed Enantioselective Heck Reactions: Synthesis of S- and P-Stereogenic Heterocycles.

    PubMed

    de Azambuja, Francisco; Carmona, Rafaela C; Chorro, Tomaz H D; Heerdt, Gabriel; Correia, Carlos Roque D

    2016-08-01

    S- and P-Stereogenic heterocycles were synthesized by a remarkably simple enantioselective Heck desymmetrization reaction based on the unprecedented noncovalent directing effect of S=O and P=O functionalities. Selected prochiral symmetric substrates were efficiently arylated using the recently disclosed chiral PyraBOx ligand under mild and open-flask reaction conditions. Several five-membered aryl- sulfones, sulfoxides, and phosphine oxides were synthesized in good to excellent yields, in good to high diastereoselectivity, and enantiomeric ratios up to 98:2. Theoretical calculations also support the noncovalent directing effect of the S=O and P=O functionalities during the arylation process.

  18. Electrical Property of Conventionally Sintered ZnO

    NASA Astrophysics Data System (ADS)

    Tak, S. K.; Shekhwat, M. S.; Mangal, R.

    ZnO powder was synthesized by solid state reaction method. The synthesized powder was granulated and pressed using uni-axial press for preparing the pallets. The prepared pellets were sintered in conventional furnace at different temperatures (900-1300° C). The phase study was done by powder X-ray diffraction and it was found that the there is no other phase present in the synthesized material but the peak intensity is increasing with temperature. The crystallite size of the synthesized ZnO powder was found to be increase with temperature. The effect of sintering on grain growth is investigated by scanning electron microscopy (SEM). SEM revels that the average grain size is increases with increase in sintering temperature. AC impedance of these samples was decreased markedly with increased sintering temperature. In present work the effect of sintering temperatures and hold time on micro structural and electrical properties of ZnO ceramics is carried out.

  19. Field assisted sintering of ceramic materials

    NASA Astrophysics Data System (ADS)

    Stanciu, Lia Antoaneta

    2003-06-01

    The objective of this dissertation is to provide an understanding of the processing mechanisms of ceramic materials under an electrical field. Different parameters of the process, such as the electrical field, the heating rate, the holding time, and the precursor powder characteristics are studied in connection with their individual effect on the microstructural evolution and properties. The work reviews the fundamentals of sintering in the presence and in the absence of an electrical field, electrical conductivity in ceramics, precursor powder preparation methods for ceramic processing, as well as the relationship between the thermal properties and the neck formation in the first sintering stage. The ceramic materials that are chosen for the sintering studies are: Al2O3, TiO2, Al2TiO5 and MoSi2. Two type of precursors are used for the studies on Al 2TiO5: an amorphous sol-gel nanosize, and a crystalline coprecipitated micron size powder. Comparative studies on the effect of the heating rates in FAST on the conductive MoSi2 versus non-conductive Al2 O3 are also presented. The initial sintering stages of alpha-Al 2O3, which displays the maximum sintering activity under electrical field, are studied by a thermo-optical measurement method (TOM). The TOM method measures in-situ the thermal diffusivity of the powder. All the materials are characterized after sintering by XRD, FTIR, SEM, TEM, density and thermal diffusivity by TOM. The results show that the electrical field application enhances the kinetics of non-conductive oxide ceramics (Al2TiO5) formation by reaction sintering of the individual oxides. It also increases the rate of the neck formation during first sintering stage, and reduces porosity, thus improving the final density of non-conductive Al2O3. The sol-gel precursor powders with nanosize particles and a higher degree of homogeneity result in improved densification of the final consolidated part as compared to micron size or mechanically mixed precursors

  20. Sintering of calcium phosphate bioceramics.

    PubMed

    Champion, E

    2013-04-01

    Calcium phosphate ceramics have become of prime importance for biological applications in the field of bone tissue engineering. This paper reviews the sintering behaviour of these bioceramics. Conventional pressureless sintering of hydroxyapatite, Ca10(PO4)6(OH)2, a reference compound, has been extensively studied. Its physico-chemistry is detailed. It can be seen as a competition between two thermally activated phenomena that proceed by solid-state diffusion of matter: densification and grain growth. Usually, the objective is to promote the first and prevent the second. Literature data are analysed from sintering maps (i.e. grain growth vs. densification). Sintering trajectories of hydroxyapatite produced by conventional pressureless sintering and non-conventional techniques, including two-step sintering, liquid phase sintering, hot pressing, hot isostatic pressing, ultrahigh pressure, microwave and spark plasma sintering, are presented. Whatever the sintering technique may be, grain growth occurs mainly during the last step of sintering, when the relative bulk density reaches 95% of the maximum value. Though often considered very advantageous, most assisted sintering techniques do not appear very superior to conventional pressureless sintering. Sintering of tricalcium phosphate or biphasic calcium phosphates is also discussed. The chemical composition of calcium phosphate influences the behaviour. Similarly, ionic substitutions in hydroxyapatite or in tricalcium phosphate create lattice defects that modify the sintering rate. Depending on their nature, they can either accelerate or slow down the sintering rate. The thermal stability of compounds at the sintering temperature must also be taken into account. Controlled atmospheres may be required to prevent thermal decomposition, and flash sintering techniques, which allow consolidation at low temperature, can be helpful.

  1. Evaluation of sintering effects on SiC incorporated UO2 kernels under Ar and Ar-4%H2 environments

    SciTech Connect

    Silva, Chinthaka M; Lindemer, Terrence; Hunt, Rodney Dale; Collins, Jack Lee; Terrani, Kurt A; Snead, Lance Lewis

    2013-01-01

    Silicon carbide (SiC) is suggested as an oxygen getter in UO2 kernels used for TRISO particle fuels to lower oxygen potential and prevent kernel migration during irradiation. Scanning electron microscopy and X-ray diffractometry analyses performed on sintered kernels verified that internal gelation process can be used to incorporate SiC in urania fuel kernels. Sintering in either Ar or Ar-4%H2 at 1500 C lowered the SiC content in the UO2 kernels to some extent. Formation of UC was observed as the major chemical phase in the process, while other minor phases such as U3Si2C2, USi2, U3Si2, and UC2 were also identified. UC formation was presumed to be occurred by two reactions. The first was the SiC reaction with its protective SiO2 oxide layer on SiC grains to produce volatile SiO and free carbon that subsequently reacted with UO2 to form UC. The second process was direct UO2 reaction with SiC grains to form SiO, CO, and UC, especially in Ar-4%H2. A slightly higher density and UC content was observed in the sample sintered in Ar-4%H2, but the use of both atmospheres produced kernels with ~95% of theoretical density. It is suggested that incorporating CO in the sintering gas would prevent UC formation and preserve the initial SiC content.

  2. Investigation of photochemical reaction products of glucose formed during direct UV detection in CE.

    PubMed

    Schmid, Thomas; Himmelsbach, Markus; Buchberger, Wolfgang W

    2016-04-01

    In CE, saccharides are accessible to direct UV detection due to a photochemical reaction in the detection window of the separation capillary resulting in the formation of UV absorbing substances. Employing a CE method that allows long in-capillary irradiation with subsequent UV and MS detection, the present study could identify several reaction products of glucose. Among these were UV absorbing substances so far unknown to be formed during direct UV detection with the chemical formulas C4 H6 O2 , C5 H6 O4 , C5 H8 O3, and C6 H8 O5 . Investigations of the impact of the irradiation time revealed differences between these reaction products suggesting differing reaction mechanisms especially for the smallest products. More detailed information could be obtained by experiments with isotope-labeled substrates performed to determine the parts of glucose that are converted to the particular reaction products. In addition, structural formulas for the reaction products were suggested based on HPLC-MS/MS measurements of off-line irradiated glucose solutions which revealed the existence of functional groups such as carboxylic acid or aldehyde groups.

  3. Sintering of Synroc D

    SciTech Connect

    Robinson, G.

    1982-06-01

    Sintering has been investigated as a method for the mineralization and densification of high-level nuclear defense waste powder. Studies have been conducted on Synroc D composite powder LS04. Optimal densification has been found to be highly dependent on the characteristics of the starting material. Powder subjected to milling, which was believed to reduce the level of agglomeration and possibly particle size, was found to densify better than powder not subjected to this milling. Densities of greater than 95% of theoretical could be achieved for samples sintered at 1150 to 1200/sup 0/C. Mineralogy was found to be as expected for Synroc D for samples sintered in a CO/sub 2//CO atmosphere where the Fe/sup +2//Fe/sup +3/ ratio was maintained at 1.0 to 5.75. In a more oxidizing, pure CO/sub 2/ atmosphere a new phase, not previously identified in Synroc D, was found.

  4. Acylsilanes in Iridium-Catalyzed Directed Amidation Reactions and Formation of Heterocycles via Siloxycarbenes.

    PubMed

    Becker, Peter; Pirwerdjan, Ramona; Bolm, Carsten

    2015-12-14

    Exposing ortho-amido aroylsilanes to visible light or heat leads to cyclization reactions that provide N-heterocyclic compounds via siloxycarbenes as key intermediates. The previously unreported starting materials have been prepared by directed amidations of aromatic acylsilanes in the presence of an iridium catalyst followed by N-alkylation.

  5. A unified understanding of (γ, n) and (n, γ) reactions and direct neutron-multiplicity sorting

    NASA Astrophysics Data System (ADS)

    Utsunomiya, Hiroaki; Goriely, Stephane; m, Therese Renstrø; Katayama, Seitaro; Gheorghe, Ioana; Filipescu, Dan; Belyshev, Sergey; Varlamov, Vladimir

    2017-09-01

    We discuss the γ-ray strength function toward a unified understanding of (γ,n) and (n,γ) reactions and propose a novel technique of direct neutron-multiplicity sorting to resolve the long-standing discrepancy between the Livermore and Scalya data of partial photoneutron cross sections.

  6. Online mutability of step direction during rapid stepping reactions evoked by postural perturbation.

    PubMed

    Tripp, Bryan P; McIlroy, William E; Maki, Brian E

    2004-03-01

    Stepping reactions are often triggered rapidly in response to loss of balance. It has been unclear whether spatial step parameters are defined at time of step-initiation or whether they can be modulated online, during step execution, in response to sensory feedback about the evolving state of instability. This study explored the capacity to actively alter step direction subsequent to step initiation in six healthy young-adult subjects. To elicit forward-step reactions, subjects were released suddenly from a tethered forward lean. A second perturbation (medio-lateral support-surface translation) was applied at lags of 0-200 ms. Active reaction to the second perturbation was determined primarily through analysis of swing-leg hip-abductor activation. In addition, to gauge the biomechanical consequence of the changes in muscle activation, we compared the measured medio-lateral swing-foot displacement to that predicted by a simple passive mechanical model. Perturbations at 0-100 ms lag evoked active medio-lateral swing-foot deviation, allowing balance to be recovered with a single step. However, when the second perturbation occurred near foot-off (200-ms lag), there was no evidence of active alteration of step direction and subjects typically required additional steps to recover balance. The results suggest that step direction can be reparameterized during early stages of stepping reactions, but that step direction was not actively modulated in response to perturbation arising near start of swing phase.

  7. Some acyclic analogues of nucleotides and their template-directed reactions

    NASA Technical Reports Server (NTRS)

    Tohidi, Mahrokh; Orgel, Leslie E.

    1989-01-01

    Bismonophosphoimidazolides of acyclic analogues of guanosine IV and adenosine V were synthesized. They undergo oligomerization in the presence of complementary polynucleotide templates. Details of their synthesis and their subsequent template- and nontemplate-directed reactions are described, and their possible relevance to the origin of life is discussed.

  8. Expanding the enzyme universe: accessing non-natural reactions by mechanism-guided directed evolution.

    PubMed

    Renata, Hans; Wang, Z Jane; Arnold, Frances H

    2015-03-09

    High selectivity and exquisite control over the outcome of reactions entice chemists to use biocatalysts in organic synthesis. However, many useful reactions are not accessible because they are not in nature's known repertoire. In this Review, we outline an evolutionary approach to engineering enzymes to catalyze reactions not found in nature. We begin with examples of how nature has discovered new catalytic functions and how such evolutionary progression has been recapitulated in the laboratory starting from extant enzymes. We then examine non-native enzyme activities that have been exploited for chemical synthesis, with an emphasis on reactions that do not have natural counterparts. Non-natural activities can be improved by directed evolution, thus mimicking the process used by nature to create new catalysts. Finally, we describe the discovery of non-native catalytic functions that may provide future opportunities for the expansion of the enzyme universe.

  9. Expanding the Enzyme Universe: Accessing Non-Natural Reactions by Mechanism-Guided Directed Evolution

    PubMed Central

    Renata, Hans; Wang, Z. Jane

    2015-01-01

    High selectivities and exquisite control over reaction outcomes entice chemists to use biocatalysts in organic synthesis. However, many useful reactions are not accessible because they are not in nature’s known repertoire. We will use this review to outline an evolutionary approach to engineering enzymes to catalyze reactions not found in nature. We begin with examples of how nature has discovered new catalytic functions and how such evolutionary progressions have been recapitulated in the laboratory starting from extant enzymes. We then examine non-native enzyme activities that have been discovered and exploited for chemical synthesis, emphasizing reactions that do not have natural counterparts. The new functions have mechanistic parallels to the native reaction mechanisms that often manifest as catalytic promiscuity and the ability to convert from one function to the other with minimal mutation. We present examples of how non-natural activities have been improved by directed evolution, mimicking the process used by nature to create new catalysts. Examples of new enzyme functions include epoxide opening reactions with non-natural nucleophiles catalyzed by a laboratory-evolved halohydrin dehalogenase, cyclopropanation and other carbene transfer reactions catalyzed by cytochrome P450 variants, and non-natural modes of cyclization by a modified terpene synthase. Lastly, we describe discoveries of non-native catalytic functions that may provide future opportunities for expanding the enzyme universe. PMID:25649694

  10. Direct observation of ferromagnetism in grain boundary phase of Nd-Fe-B sintered magnet using soft x-ray magnetic circular dichroism

    SciTech Connect

    Nakamura, T.; Yasui, A.; Kotani, Y.; Iwai, H.; Akiya, T.; Ohkubo, T.; Hono, K.; Hirosawa, S.; Gohda, Y.

    2014-11-17

    We have investigated the magnetism of the grain boundary (GB) phase in a Nd{sub 14.0}Fe{sub 79.7}Cu{sub 0.1}B{sub 6.2} sintered magnet using soft x-ray magnetic circular dichroism (XMCD) at the Fe L{sub 2,3}-edges. Soft XMCD spectra were measured from the fractured surface that was confirmed to be covered with a thin GB phase by Auger electron spectroscopy. The magnetic moment of Fe in the GB phase was estimated to be m{sub GB}=1.4 μ{sub B} at 30 °C using the sum rule analysis for XMCD spectra, which is 60% of that of Fe in the Nd{sub 2}Fe{sub 14}B compound. The temperature dependence of m{sub GB} evaluated with reference to Fe in the Nd{sub 2}Fe{sub 14}B phase indicated that the Curie temperature of the GB phase is more than 50 °C lower compared to that of Nd{sub 2}Fe{sub 14}B.

  11. Reduction reaction analysis of nanoparticle copper oxide for copper direct bonding using formic acid

    NASA Astrophysics Data System (ADS)

    Fujino, Masahisa; Akaike, Masatake; Matsuoka, Naoya; Suga, Tadatomo

    2017-04-01

    Copper direct bonding is required for electronics devices, especially power devices, and copper direct bonding using formic acid is expected to lower the bonding temperature. In this research, we analyzed the reduction reaction of copper oxide using formic acid with a Pt catalyst by electron spin resonance analysis and thermal gravimetry analysis. It was found that formic acid was decomposed and radicals were generated under 200 °C. The amount of radicals generated was increased by adding the Pt catalyst. Because of these radicals, both copper(I) oxide and copper(II) oxide start to be decomposed below 200 °C, and the reduction of copper oxide is accelerated by reactants such as H2 and CO from the decomposition of formic acid above 200 °C. The Pt catalyst also accelerates the reaction of copper oxide reduction. Herewith, it is considered that the copper surface can be controlled more precisely by using formic acid to induce direct bonding.

  12. Bond selectivity in electron-induced reaction due to directed recoil on an anisotropic substrate

    NASA Astrophysics Data System (ADS)

    Anggara, Kelvin; Huang, Kai; Leung, Lydie; Chatterjee, Avisek; Cheng, Fang; Polanyi, John C.

    2016-12-01

    Bond-selective reaction is central to heterogeneous catalysis. In heterogeneous catalysis, selectivity is found to depend on the chemical nature and morphology of the substrate. Here, however, we show a high degree of bond selectivity dependent only on adsorbate bond alignment. The system studied is the electron-induced reaction of meta-diiodobenzene physisorbed on Cu(110). Of the adsorbate's C-I bonds, C-I aligned `Along' the copper row dissociates in 99.3% of the cases giving surface reaction, whereas C-I bond aligned `Across' the rows dissociates in only 0.7% of the cases. A two-electronic-state molecular dynamics model attributes reaction to an initial transition to a repulsive state of an Along C-I, followed by directed recoil of C towards a Cu atom of the same row, forming C-Cu. A similar impulse on an Across C-I gives directed C that, moving across rows, does not encounter a Cu atom and hence exhibits markedly less reaction.

  13. Direct measurement of the 22Ne(p,γ)23Na reaction cross section at LUNA

    NASA Astrophysics Data System (ADS)

    Ferraro, Federico; LUNA Collaboration

    2016-06-01

    The 22Ne(p, γ)23Na reaction takes part in the NeNa cycle of hydrogen burning, influencing the production of the elements between 20Ne and 27Al in red giant stars, asymptotic giant stars and classical novae. The 22Ne(p,γ)27Na reaction rate is very uncertain because of a large number of tentative resonances in the Gamow window, where only upper limits were quoted in literature. A direct measurement of the 22Ne(p, γ)23Na reaction cross section has been carried out at LUNA using a windowless differential-pumping gas target with two high- purity germanium (HPGe) detectors. A new measurement with a 4π bismuth germanate (BGO) summing detector is ongoing. During the HPGe phase of the experiment the strengths of the resonances at 156.2 keV, 189.5 keV and 259.7 keV have been directly measured for the first time and their contribution to the reaction rate has been calculated. The decay scheme of the newly discovered resonances has been established as well and some improved upper limits on the unobserved resonances have been put. The BGO detector with its 70% γ-detection efficiency allows to measure the cross section at lower energy. In order to further investigate the resonances at 71 keV and 105 keV and the direct-capture component, the data taking is ongoing.

  14. Direct detection of pyridine formation by the reaction of CH (CD) with pyrrole: a ring expansion reaction

    SciTech Connect

    Soorkia, Satchin; Taatjes, Craig A.; Osborn, David L.; Selby, Talitha M.; Trevitt, Adam J.; Wilson, Kevin R.; Leone, Stephen R.

    2010-03-16

    The reaction of the ground state methylidyne radical CH (X2Pi) with pyrrole (C4H5N) has been studied in a slow flow tube reactor using Multiplexed Photoionization Mass Spectrometry coupled to quasi-continuous tunable VUV synchrotron radiation at room temperature (295 K) and 90 oC (363 K), at 4 Torr (533 Pa). Laser photolysis of bromoform (CHBr3) at 248 nm (KrF excimer laser) is used to produce CH radicals that are free to react with pyrrole molecules in the gaseous mixture. A signal at m/z = 79 (C5H5N) is identified as the product of the reaction and resolved from 79Br atoms, and the result is consistent with CH addition to pyrrole followed by Helimination. The Photoionization Efficiency curve unambiguously identifies m/z = 79 as pyridine. With deuterated methylidyne radicals (CD), the product mass peak is shifted by +1 mass unit, consistent with the formation of C5H4DN and identified as deuterated pyridine (dpyridine). Within detection limits, there is no evidence that the addition intermediate complex undergoes hydrogen scrambling. The results are consistent with a reaction mechanism that proceeds via the direct CH (CD) cycloaddition or insertion into the five-member pyrrole ring, giving rise to ring expansion, followed by H atom elimination from the nitrogen atom in the intermediate to form the resonance stabilized pyridine (d-pyridine) molecule. Implications to interstellar chemistry and planetary atmospheres, in particular Titan, as well as in gas-phase combustion processes, are discussed.

  15. Photochemical Reactions of Particulate Organic Matter: Deciphering the Role of Direct and Indirect Processes

    NASA Astrophysics Data System (ADS)

    Carrasquillo, A. J.; Gelfond, C. E.; Kocar, B. D.

    2016-12-01

    Photochemical reactions of natural organic matter (NOM) represent potentially important pathways for biologically recalcitrant material to be chemically altered in aquatic systems. Irradiation can alter the physical state of organic matter by facilitating the cycling between the particulate (POM) and dissolved (DOM) pools, however, a molecular level understanding of this chemically dynamic system is currently lacking. Photochemical reactions of a target molecule proceed by the direct absorption of a photon, or through reaction with a second photolytically generated species (i.e. the hydroxyl radical, singlet oxygen, excited triplet state NOM, hydrogen peroxide, etc.). Here, we isolate the major direct and indirect photochemical reactions of a lignocellulose-rich POM material (Phragmites australis) to determine their relative importance in changing the the chemical structure of the parent POM, and in the production of DOM. We measured POM molecular structure using a combination of NMR and FTIR for bulk analyses and scanning transmission x-ray microscopy (STXM) for spatially resolved chemistry, while the chemical composition of photo-produced DOM was measured using ultra-high resolution mass spectrometry. Results are discussed in the context of the differences in chemical composition of both NOM pools resulting from the isolated photochemical pathways. All treatments result in an increase in DOM with reaction time, indicating that the larger POM matrix is likely fragmenting into smaller more soluble species. Spectroscopic measurements, on the other hand, point to functionalization reactions which increase the abundance of alcohol, acid, and carbonyl moieties in both carbon pools. This unique dataset provides new insight into how photochemical reactions alter the chemical composition of NOM while highlighting the relative importance of indirect pathways.

  16. Direct detection of hepatitis B virus from dried blood spots by polymerase chain reaction amplification.

    PubMed Central

    Gupta, B P; Jayasuryan, N; Jameel, S

    1992-01-01

    The presence of hepatitis B virus DNA in the sera of individuals is the most definitive marker of an active viral infection. We have used polymerase chain reaction detection of hepatitis B virus DNA directly on whole blood dried as a spot on filter paper. The method is rapid, specific, and sensitive and has the ability to detect as little as 10 virus particles by ethidium bromide staining of the polymerase chain reaction-amplified products. The method is cost-effective, and the stability of the spots makes the collection and transportation of potentially infectious blood safe. Images PMID:1500493

  17. Network structural analysis using directed graph for chemical reaction analysis in weakly-ionized plasmas

    NASA Astrophysics Data System (ADS)

    Nobuto, Kyosuke; Mizui, Yasutaka; Miyagi, Shigeyuki; Sakai, Osamu; Murakami, Tomoyuki

    2016-09-01

    We visualize complicated chemical reaction systems in weakly-ionized plasmas by analysing network structure for chemical processes, and calculate some indexes by assuming interspecies relationships to be a network to clarify them. With the current social evolution, the mean size of general data which we can use in computers grows huge, and significance of the data analysis increases. The methods of the network analysis which we focus on in this study do not depend on a specific analysis target, but the field where it has been already applied is still limited. In this study, we analyse chemical reaction systems in plasmas for configuring the network structure. We visualize them by expressing a reaction system in a specific plasma by a directed graph and examine the indexes and the relations with the characteristic of the species in the reaction system. For example, in the methane plasma network, the centrality index reveals importance of CH3 in an influential position of species in the reaction. In addition, silane and atmospheric pressure plasmas can be also visualized in reaction networks, suggesting other characteristics in the centrality indexes.

  18. Reactive sintering and reactive hot

    NASA Astrophysics Data System (ADS)

    Murray, J. C.; German, R. M.

    1992-09-01

    NbAl3 has been synthesized from elemental powders by reactive sintering (RS) and reactive hot isostatic pressing (RHIP). Both processes involve a self-propagating exothermic reaction between the constituent powders to form an intermetallic compound. The RHIP approach uses simultaneous external pressurization to make a higher density product. This study focused on developing a method to use reactive synthesis to form high-density NbAl3 compacts. High RS and RHIP densities were possible with the appropriate raw materials and processing parameters. These include powder purity, particle sizes, degassing, heating rate, furnace temperature, and compaction pressures. Near full density was attained with RHIP, and up to 95 pct density was attained with RS.

  19. Extrusion of spark plasma sintered aluminum-carbon nanotube composites at various sintering temperatures.

    PubMed

    Kwon, Hansang; Kawasaki, Akira

    2009-11-01

    The combined processes of spark plasma sintering and hot extrusion were used to fabricate a multi-walled carbon nanotube (MWCNT) reinforced aluminum (Al) matrix composite. The structural defects of carbon nanotubes (CNT) at various sintering temperatures were investigated by Raman spectroscopy. A small amount of Al liquid phase was generated and it reacted with disordered CNTs, even during the solid-state spark plasma sintering process. The influence of Al carbides generated by the reaction between Al and disordered CNTs is discussed from a microstructural viewpoint and in relation to tensile strength. We conclude that structurally controlled CNTs could potentially be attractive for metal matrix applications, and could significantly improve the mechanical properties of AI-CNT composites.

  20. DIRECT COMPARISON OF KINETIC AND LOCAL EQUILIBRIUM FORMULATIONS FOR SOLUTE TRANSPORT AFFECTED BY SURFACE REACTIONS.

    USGS Publications Warehouse

    Bahr, Jean M.; Rubin, Jacob

    1987-01-01

    Modeling transport of reacting solutes in porous media often requires a choice between models based on the local equilibrium assumption (LEA) and models involving reaction kinetics. Direct comparison of the mathematical formulations for these two types of transport models can aid in this choice. For cases of transport affected by surface reaction, such a comparison is made possible by a new derivation procedure. This procedure yields a kinetics-based formulation that is the sum of the LEA formulation and one or more kinetically influenced terms. The dimensionless form of the new kinetics-based formulation facilitates identification of critical parameter groupings which control the approach to transport behavior consistent with LEA model predictions. Results of numerical experiments demonstrate that criteria for LEA applicability can be expressed conveniently in terms of these parameter groupings. The derivation procedure is demonstrated for examples of surface reactions including first-order reversible sorption, Langmuir-type kinetics and binary, homovalent ion exchange.

  1. Synthetic Studies on Tricyclic Diterpenoids: Direct Allylic Amination Reaction of Isopimaric Acid Derivatives.

    PubMed

    Timoshenko, Mariya A; Kharitonov, Yurii V; Shakirov, Makhmut M; Bagryanskaya, Irina Yu; Shults, Elvira E

    2016-02-01

    A selective synthesis of 7- or 14-nitrogen containing tricyclic diterpenoids was completed according to a strategy in which the key step was the catalyzed direct allylic amination of methyl 14α-hydroxy-15,16-dihydroisopimarate with a wide variety of nitrogenated nucleophiles. It was revealed that the selectivity of the reaction depends on the nature of nucleophile. The catalyzed reaction of the mentioned diterpenoid allylic alcohol with 3-nitroaniline, 3-(trifluoromethyl)aniline, and 4-(trifluoromethyl)aniline yield the subsequent 7α-, 7β- and 14αnitrogen-containing diterpenoids. The reaction with 2-nitroaniline, 4-nitro-2-chloroaniline, 4-methoxy-2-nitroaniline, phenylsulfamide, or tert-butyl carbamate proceeds with the formation of 7α-nitrogen-substituted diterpenoids as the main products.

  2. Atmospheric chemistry. Direct kinetic measurement of the reaction of the simplest Criegee intermediate with water vapor.

    PubMed

    Chao, Wen; Hsieh, Jun-Ting; Chang, Chun-Hung; Lin, Jim Jr-Min

    2015-02-13

    Carbonyl oxides, or Criegee intermediates, are important transient species formed in the reactions of unsaturated hydrocarbons with ozone. Although direct detection of Criegee intermediates has recently been realized, the main atmospheric sink of Criegee intermediates remains unclear. We report ultraviolet absorption spectroscopic measurements of the lifetime of the simplest Criegee intermediate, CH2OO, at various relative humidity levels up to 85% at 298 kelvin. An extremely fast decay rate of CH2OO was observed at high humidity. The observed quadratic dependence of the decay rate on water concentration implied a predominant reaction with water dimer. On the basis of the water dimer equilibrium constant, the effective rate coefficient of the CH2OO + (H2O)2 reaction was determined to be 6.5 (±0.8) × 10(-12) cubic centimeters per second. This work would help modelers to better constrain the atmospheric concentrations of CH2OO.

  3. Synthetic Studies on Tricyclic Diterpenoids: Direct Allylic Amination Reaction of Isopimaric Acid Derivatives†

    PubMed Central

    Timoshenko, Mariya A.; Kharitonov, Yurii V.; Shakirov, Makhmut M.; Bagryanskaya, Irina Yu.

    2015-01-01

    Abstract A selective synthesis of 7‐ or 14‐nitrogen containing tricyclic diterpenoids was completed according to a strategy in which the key step was the catalyzed direct allylic amination of methyl 14α‐hydroxy‐15,16‐dihydroisopimarate with a wide variety of nitrogenated nucleophiles. It was revealed that the selectivity of the reaction depends on the nature of nucleophile. The catalyzed reaction of the mentioned diterpenoid allylic alcohol with 3‐nitroaniline, 3‐(trifluoromethyl)aniline, and 4‐(trifluoromethyl)aniline yield the subsequent 7α‐, 7β‐ and 14αnitrogen‐containing diterpenoids. The reaction with 2‐nitroaniline, 4‐nitro‐2‐chloroaniline, 4‐methoxy‐2‐nitroaniline, phenylsulfamide, or tert‐butyl carbamate proceeds with the formation of 7α‐nitrogen‐substituted diterpenoids as the main products. PMID:27308214

  4. Microwave versus conventional sintering of silicon carbide tiles

    SciTech Connect

    Kass, M.D.; Caughman, J.B.O.; Forrester, S.C.; Akerman, A.

    1997-05-07

    Silicon carbide is being evaluated as an armor material because of its lightweight, high-hardness, and excellent armor efficiency. However, one of the problems associated with silicon carbide is the high cost associated with achieving fully dense tiles. Full density requires either hot pressing and sintering or reaction bonding. Past efforts have shown that hot pressed tiles have a higher armor efficiency than those produced by reaction bonded sintering. An earlier stuy showed that the acoustic properties of fully-dense silicon carbide tiles were enhanced through the use of post-sintered microwave heat treatments. One of the least expensive forming techniques is to isostatically press-and-sinter. In this study, the authors have used microwave energy to densify silicon carbide green bodies. Microwave sintering has been demonstrated to be a very quick way to sinter ceramics such as alumina to exceptionally high densities. Previous work has shown that microwave post treatment of fully-dense reaction bonded silicon carbide tiles significantly improves the acoustic properties of the tiles. These properties include Poisson`s ratio, Young`s modulus, shear modulus, and bulk modulus.

  5. Microwave sintering versus conventional sintering of NiCuZn ferrites. Part I: Densification evolution

    NASA Astrophysics Data System (ADS)

    Zhu, Jianhua; Ouyang, Chenxin; Xiao, Shumin; Gao, Yongyi

    2016-06-01

    This work reports the recent study on the microwave sintering (MS) versus conventional sintering (CS) of NiCuZn ferrites, with particular interests in the densification evolution. NiCuZn ferrite powders were synthesized through the solid state reaction route. Densification behaviors of ferrite samples under the two types of thermal sources were monitored in real-time. Meanwhile, the influences of additives (1 wt% BSZ glass or 1 wt% Bi2O3) on the densifications were also investigated. Both constant heating rate (CHR) and master sintering curve (MSC) models were used to evaluate the sintering activation energy (Q). Results demonstrated that the microwave-enhanced diffusion mainly occurs at the intermediate sintering stage. The Q-value estimated by MSC method agreed well with that from CHR method. With the influence of microwave electromagnetic field, the activation energy of NiCuZn ferrites was decreased by roughly 100-150 kJ/mol. In addition, doping a small amount of additives could improve densification degree and reduce the minimal energy to activate diffusion mechanisms.

  6. Partial reactions and chemical rescue of site-directed mutants of Rubisco as mechanistic probes

    SciTech Connect

    Harpel, M.R.; Larimer, F.W.; Lee, E.H.; Mural, R.J.; Smith, H.B.; Soper, T.S.; Hartman, F.C.

    1991-01-01

    Given the current state of knowledge of the reaction pathways catalyzed by D-ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) and the elucidation of the three-dimensional structure of several different forms of the enzyme, sit-directed mutagenesis offers the potential to decipher catalytic roles of active-site residues and to unravel the functional significance of various structural elements. Especially intriguing are intersubunit, electrostatic interactions at the active site between Glu48 and Lys168 of the nonactivated (noncarbamylated) enzyme and between Glu48 and Lys329 of the activated (carbamylated) enzyme. In this paper, we describe two approaches to address the roles of electrostatic interactions at the active site and the roles of the participant residues: (1) characterization of pertinent site-directed mutants, including their abilities to catalyze partial reactions and (2) subtle alteration of the active-site microenvironment by manipulation of these proteins with exogenous reagents.

  7. Partial reactions and chemical rescue of site-directed mutants of Rubisco as mechanistic probes

    SciTech Connect

    Harpel, M.R.; Larimer, F.W.; Lee, E.H.; Mural, R.J.; Smith, H.B.; Soper, T.S.; Hartman, F.C.

    1991-12-31

    Given the current state of knowledge of the reaction pathways catalyzed by D-ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) and the elucidation of the three-dimensional structure of several different forms of the enzyme, sit-directed mutagenesis offers the potential to decipher catalytic roles of active-site residues and to unravel the functional significance of various structural elements. Especially intriguing are intersubunit, electrostatic interactions at the active site between Glu48 and Lys168 of the nonactivated (noncarbamylated) enzyme and between Glu48 and Lys329 of the activated (carbamylated) enzyme. In this paper, we describe two approaches to address the roles of electrostatic interactions at the active site and the roles of the participant residues: (1) characterization of pertinent site-directed mutants, including their abilities to catalyze partial reactions and (2) subtle alteration of the active-site microenvironment by manipulation of these proteins with exogenous reagents.

  8. The direct oxidative diene cyclization and related reactions in natural product synthesis

    PubMed Central

    2016-01-01

    Summary The direct oxidative cyclization of 1,5-dienes is a valuable synthetic method for the (dia)stereoselective preparation of substituted tetrahydrofurans. Closely related reactions start from 5,6-dihydroxy or 5-hydroxyalkenes to generate similar products in a mechanistically analogous manner. After a brief overview on the history of this group of transformations and a survey on mechanistic and stereochemical aspects, this review article provides a summary on applications in natural product synthesis. Moreover, current limitations and future directions in this area of chemistry are discussed. PMID:27829917

  9. Direct extraction of bacterial plasmids from food for polymerase chain reaction amplification.

    PubMed Central

    Andersen, M R; Omiecinski, C J

    1992-01-01

    In this report we describe a simple and rapid technique using DNA affinity columns that permits direct extraction of bacterial plasmids from a variety of foods for polymerase chain reaction amplification. The procedure was used to detect virulent enteroinvasive Escherichia coli in several artificially seeded matrices, including seafoods, greens, dairy products, enrichment media, and water. Polymerase inhibitors present in both foods and enrichment media were removed efficiently. Images PMID:1476448

  10. The direct reaction field hamiltonian: Analysis of the dispersion term and application to the water dimer

    NASA Astrophysics Data System (ADS)

    Thole, B. T.; Van Duijnen, P. Th.

    1982-10-01

    The induction and dispersion terms obtained from quantum-mechanical calculations with a direct reaction field hamiltonian are compared to second order perturbation theory expressions. The dispersion term is shown to give an upper bound which is a generalization of Alexander's upper bound. The model is illustrated by a calculation on the interactions in the water dimer. The long range Coulomb, induction and dispersion interactions are reasonably reproduced.

  11. Direct determination of ephedrine intermediate in a biotransformation reaction using infrared spectroscopy and PLS.

    PubMed

    Trevisan, Marcello G; Poppi, Ronei J

    2008-05-30

    Fourier transform mid-infrared spectroscopy (FT-MIR) coupled with a homemade attenuated total reflectance (ATR) flow-cell was used for on-line monitoring of a biotransformation reaction. The reaction was also monitored off-line by gas chromatography-mass spectrometry (GC-MS) enabling to establish a multivariate model for the infrared data based on partial least squares (PLS) regression. The method developed allowed the simultaneous determination of the substrate, two intermediates and the final product involved in the reduction reaction of 1-phenyl 1,2-propanedione at an initial concentration of 0.5% (v/v). The reaction was accomplished with a whole-cell suspension of Saccharomyces cerevisiae in a phosphate buffer of pH 3.0 at 32+/-1 degrees C. The ATR infrared monitoring was performed directly on the suspension cell without any separation process or extraction over 3h, totaling 188 spectra. The data were split into two subsets, with 158 times for calibration and 30 times for validation. The results showed that the proposed method may be used for on-line monitoring of the biotransformation reactions when the initial concentration is very low.

  12. Direct numerical simulation study of statistically stationary propagation of a reaction wave in homogeneous turbulence

    NASA Astrophysics Data System (ADS)

    Yu, Rixin; Lipatnikov, Andrei N.

    2017-06-01

    A three-dimensional (3D) direct numerical simulation (DNS) study of the propagation of a reaction wave in forced, constant-density, statistically stationary, homogeneous, isotropic turbulence is performed by solving Navier-Stokes and reaction-diffusion equations at various (from 0.5 to 10) ratios of the rms turbulent velocity U' to the laminar wave speed, various (from 2.1 to 12.5) ratios of an integral length scale of the turbulence to the laminar wave thickness, and two Zeldovich numbers Ze=6.0 and 17.1. Accordingly, the Damköhler and Karlovitz numbers are varied from 0.2 to 25.1 and from 0.4 to 36.2, respectively. Contrary to an earlier DNS study of self-propagation of an infinitely thin front in statistically the same turbulence, the bending of dependencies of the mean wave speed on U' is simulated in the case of a nonzero thickness of the local reaction wave. The bending effect is argued to be controlled by inefficiency of the smallest scale turbulent eddies in wrinkling the reaction-zone surface, because such small-scale wrinkles are rapidly smoothed out by molecular transport within the local reaction wave.

  13. Direct dynamics study on hydrogen abstraction reaction of CF 3CHOHCF 3 with OH radical

    NASA Astrophysics Data System (ADS)

    Wang, Ying; Liu, Jing-Yao; Li, Ze-Sheng

    2007-05-01

    Dual-level direct dynamics method is employed to investigate the H-abstraction reaction CF 3CHOHCF 3 with OH radical. Two hydrogen-abstraction reaction channels are possible: one from the methylene (-CH-) position and the other from the hydroxyl (-OH) position. The minimum energy path is calculated at the B3LYP/6-311G(d,p) level, and the energetic information is further refined by a new powerful and inexpensive BMC-CCSD method. To testify the accuracy of the structures and the energies, the recently developed hybrid density functional theory BB1K and higher level MC-QCISD are applied to this system. Hydrogen-bonded complexes are presented at both reactants and products sides of these two channels, which indicating that the reaction may proceed via an indirect mechanism. The rate constants for each reaction channel are evaluated by canonical variational transition state theory (CVT) with a small-curvature tunneling correction (SCT) over a wide range of temperatures from 200 to 2000 K. The calculated CVT/SCT rate constants are in good agreement with the available experimental values in the temperature region 250-430 K. The present results indicate that the two channels are competitive. At lower temperature, the reaction occurs mainly via the hydroxyl-H-abstraction channel, while the methylene-H-abstraction channel is preferred when the temperature is higher than 273 K.

  14. Anisotropic constitutive model and FE simulation of the sintering process of slip cast traditional porcelain

    NASA Astrophysics Data System (ADS)

    Sarbandi, B.; Besson, J.; Boussuge, M.; Ryckelynck, D.

    2010-06-01

    Slip cast ceramic components undergo both sintering shrinkage and creep deformation caused by gravity during the firing cycle. In addition sintering may be anisotropic due to the development of preferential directions during slip casting. Both phenomena induce complex deformations of parts which make the design of casting molds difficult. To help solving this problem, anisotropic constitutive equations are proposed to represent the behavior of the ceramic compacts during sintering. The model parameters are identified using tests allowing to characterize both sintering and creep. The model was implemented in a finite element software and used to simulate the deformation of a traditional ceramic object during sintering.

  15. Anisotropic constitutive model and FE simulation of the sintering process of slip cast traditional porcelain

    SciTech Connect

    Sarbandi, B.; Besson, J.; Boussuge, M.; Ryckelynck, D.

    2010-06-15

    Slip cast ceramic components undergo both sintering shrinkage and creep deformation caused by gravity during the firing cycle. In addition sintering may be anisotropic due to the development of preferential directions during slip casting. Both phenomena induce complex deformations of parts which make the design of casting molds difficult. To help solving this problem, anisotropic constitutive equations are proposed to represent the behavior of the ceramic compacts during sintering. The model parameters are identified using tests allowing to characterize both sintering and creep. The model was implemented in a finite element software and used to simulate the deformation of a traditional ceramic object during sintering.

  16. Sintered composite filter

    DOEpatents

    Bergman, W.

    1986-05-02

    A particulate filter medium formed of a sintered composite of 0.5 micron diameter quartz fibers and 2 micron diameter stainless steel fibers is described. Preferred composition is about 40 vol.% quartz and about 60 vol.% stainless steel fibers. The media is sintered at about 1100/sup 0/C to bond the stainless steel fibers into a cage network which holds the quartz fibers. High filter efficiency and low flow resistance are provided by the smaller quartz fibers. High strength is provided by the stainless steel fibers. The resulting media has a high efficiency and low pressure drop similar to the standard HEPA media, with tensile strength at least four times greater, and a maximum operating temperature of about 550/sup 0/C. The invention also includes methods to form the composite media and a HEPA filter utilizing the composite media. The filter media can be used to filter particles in both liquids and gases.

  17. Sintered wire cathode

    DOEpatents

    Falce, Louis R.; Ives, R. Lawrence

    2009-06-09

    A porous cathode structure is fabricated from a plurality of wires which are placed in proximity to each other in elevated temperature and pressure for a sintering time. The sintering process produces the porous cathode structure which may be divided into a plurality of individual porous cathodes, one of which may be placed into a dispenser cathode support which includes a cavity for containing a work function reduction material such as BaO, CaO, and Al.sub.2O.sub.3. The work function reduction material migrates through the pores of the porous cathode from a work replenishment surface adjacent to the cavity of the dispenser cathode support to an emitting cathode surface, thereby providing a dispenser cathode which has a uniform work function and therefore a uniform electron emission.

  18. Magnetic properties of LiZnCu ferrite synthesized by the microwave sintering method

    NASA Astrophysics Data System (ADS)

    Khot, Sujata S.; Shinde, Neelam S.; Basavaiah, Nathani; Watawe, Shrikant C.; Vaidya, Milind M.

    2015-01-01

    Lithium ferrites have attracted considerable attention because they have been used as replacements for garnets due to their low cost. A series of polycrystalline ferrite samples were prepared with the composition of LiXZn(0.6-2X)Cu0.4Fe2O4(X=0.05, 0.1, 0.15, 0.2, 0.25, 0.3) at chemical reaction temperature 150 °C by sintering with microwave assisted combustion method. The characterization shows the formation of single phase cubic structure when carried out by using the X-rays technique and I-R technique. Magnetization parameters such as saturation magnetization, coercivity, magnetic moment were calculated by using the Hysteresis graph. The Curie temperature obtained using the susceptibility data are found to be in the range 350-700 °C. Anhysteric remanent magnetization is used for estimating the grain size and domain structure of the composition. An attempt has been made to synthesis the nano-particles at lower reaction temperature by using non-conventional microwave sintering method. The advantage of this method is its lower sintering temperature and time compared to the conventional ceramic technique and direct formation of nano-ferrites without ball-milling.

  19. SINTERING METAL OXIDES

    DOEpatents

    Roake, W.E.

    1960-09-13

    A process is given for producing uranium dioxide material of great density by preparing a compacted mixture of uranium dioxide and from 1 to 3 wt.% of calcium hydride, heating the mixture to at least 675 deg C for decomposition of the hydride and then for sintering, preferably in a vacuum, at from 1550 to 2000 deg C. Calcium metal is formed, some uranium is reduced by the calcium to the metal and a product of high density is obtained.

  20. Ab initio study of the H + HONO reaction: Direct abstraction versus indirect exchange processes

    SciTech Connect

    Hsu, C.C.; Lin, M.C.; Mebel, A.M.; Melius, C.F.

    1997-01-02

    The mechanism of the H + HONO reaction (for which no experimental data are available) has been elucidated by ab initio molecular orbital calculations using modified G2 and BAC-MP4 methods. These results indicate that the reaction occurs predominantly by two indirect metathetical processes. One produces OH + HNO and H{sub 2}O + NO from the decomposition of vibrationally excited hydroxyl nitroxide, HN(O)OH, formed by H atom addition to the N atom of HONO. The other produces H{sub 2}O + NO from the decomposition of vibrationally excited dihydroxylamino radical, N(OH){sub 2}, formed by H atom addition to the terminal O atom. These indirect displacement processes are much more efficient than the commonly assumed, direct H-abstraction reaction producing H{sub 2} + NO{sub 2}. A transition-state theory calculation for the direct abstraction reaction and RRKM calculations for the two indirect displacement processes give rise to the following rate constants, in units of cm{sup 3} molecule{sup -1} s{sup -1} for the 300-3500 K temperature range under atmospheric conditions: k{sub H(2)} = 3.33 x 10{sup -16}T{sup 1.55} exp(-3328.5/T), k{sub OH} = 9.36 x 10{sup -14}T{sup 0.86} exp(-2500.8/T), k{sub H(2)O} = 1.35 x 10{sup -17}T{sup 1.89} exp-(-1935.7/T), where the rate constant for H{sub 2}O production represents the sum from both indirect displacement reactions. 32 refs., 3 figs., 7 tabs.

  1. Liquid Phase Sintering

    NASA Technical Reports Server (NTRS)

    2004-01-01

    Industry spends billions of dollars each year on machine tools to manufacture products out of metal. This includes tools for cutting every kind of metal part from engine blocks to Shuttle main engine components. Cutting tool tips often break because of weak spots or defects in their composition. Based on a new concept called defect trapping, space offers a novel environment to study defect formation in molten metal materials as they solidify. After the return of these materials from space, researchers can evaluate the source of the defect and seek ways to eliminate them in products prepared on Earth. A widely used process for cutting tip manufacturing is liquid phase sintering. Compared to Earth-sintered samples which slump due to buoyancy induced by gravity, space samples are uniformly shaped and defects remain where they are formed. By studying metals sintered in space the US tool industry can potentially enhance its worldwide competitiveness. The Consortium for Materials Development in Space along with Wyle Labs, Teledyne Advanced Materials, and McDornell Douglas have conducted experiments in space.

  2. Direct-Reaction Studies by Particle-Gamma Coincidence Spectroscopy Using HPGe-CsI and HPGe-Si Arrays

    SciTech Connect

    Allmond, James M

    2013-01-01

    Particle- and particle- - coincidence spectroscopy has several advantages in the study of direct reactions(particularly in inverse kinematics) since it can generally allow determination of: decay paths; high-precision level energies; multipolarities of transitions; and cross sections. Techniques for studying direct reactions by particle- coincidence spectroscopy are presented for two cases: (1) heavy-ion reactions with HPGe-CsI, and (2) light-ion reactions with HPGe-Si. Future direct-reaction studies with radioactive ion beams (RIBs) will mostly involve low beam intensities and inverse kinematics (i.e., Abeam>Atarget), which eliminates the traditional use of magnetic spectrometers. Particle- coincidence spectroscopy currently provides the most viable method to study direct reactions with nuclei of any level density. In the present study, the capabilities and limitations of the technique are explored.

  3. Direct-reaction studies by particle-{gamma} coincidence spectroscopy using Csi-Hpge and Si-Hpge arrays

    SciTech Connect

    Allmond, J. M.

    2013-04-19

    Particle-{gamma} and particle-{gamma}-{gamma} coincidence spectroscopy has several advantages in the study of direct reactions (particularly in inverse kinematics) since it can generally allow determination of: decay paths; high-precision level energies; multipolarities of transitions; and cross sections. Techniques for studying direct reactions by particle-{gamma} coincidence spectroscopy are presented for two cases: (1) heavy-ion reactions with CsI-HPGe, and (2) light-ion reactions with Si-HPGe. Future direct-reaction studies with radioactive ion beams (RIBs) will mostly involve low beam intensities and inverse kinematics (i.e., A{sub beam}>A{sub target}), which eliminates the traditional use of magnetic spectrometers. Particle-{gamma} coincidence spectroscopy currently provides the most viable method to study direct reactions with nuclei of any level density. In the present study, the capabilities and limitations of the technique are explored.

  4. Direct measurement of Criegee intermediate (CH2OO) reactions with acetone, acetaldehyde, and hexafluoroacetone.

    PubMed

    Taatjes, Craig A; Welz, Oliver; Eskola, Arkke J; Savee, John D; Osborn, David L; Lee, Edmond P F; Dyke, John M; Mok, Daniel W K; Shallcross, Dudley E; Percival, Carl J

    2012-08-14

    Criegee biradicals, i.e., carbonyl oxides, are critical intermediates in ozonolysis and have been implicated in autoignition chemistry and other hydrocarbon oxidation systems, but until recently the direct measurement of their gas-phase kinetics has not been feasible. Indirect determinations of Criegee intermediate kinetics often rely on the introduction of a scavenger molecule into an ozonolysis system and analysis of the effects of the scavenger on yields of products associated with Criegee intermediate reactions. Carbonyl species, in particular hexafluoroacetone (CF(3)COCF(3)), have often been used as scavengers. In this work, the reactions of the simplest Criegee intermediate, CH(2)OO (formaldehyde oxide), with three carbonyl species have been measured by laser photolysis/tunable synchrotron photoionization mass spectrometry. Diiodomethane photolysis produces CH(2)I radicals, which react with O(2) to yield CH(2)OO + I. The formaldehyde oxide is reacted with a large excess of a carbonyl reactant and both the disappearance of CH(2)OO and the formation of reaction products are monitored. The rate coefficient for CH(2)OO + hexafluoroacetone is k(1) = (3.0 ± 0.3) × 10(-11) cm(3) molecule(-1) s(-1), supporting the use of hexafluoroacetone as a Criegee-intermediate scavenger. The reactions with acetaldehyde, k(2) = (9.5 ± 0.7) × 10(-13) cm(3) molecule(-1) s(-1), and with acetone, k(3) = (2.3 ± 0.3) × 10(-13) cm(3) molecule(-1) s(-1), are substantially slower. Secondary ozonides and products of ozonide isomerization are observed from the reactions of CH(2)OO with acetone and hexafluoroacetone. Their photoionization spectra are interpreted with the aid of quantum-chemical and Franck-Condon-factor calculations. No secondary ozonide was observable in the reaction of CH(2)OO with acetaldehyde, but acetic acid was identified as a product under the conditions used (4 Torr and 293 K).

  5. Analysis of particle growth by coalescence during liquid phase sintering

    SciTech Connect

    Takajo, S.; Kaysser, W.A.; Petzow, G.

    1984-06-01

    A statistical approach has been applied to particle coarsening during liquid phase sintering assuming direct particle coalescence as basic growth mechanism instead of Ostwald ripening. The coalescence process controlled by diffusion through the melt results in an increase of the average particle size proportional to the cube root of sintering time. After a short initial sintering interval the particle size distribution approaches a unique normalized form which is broader than forms predicted by Ostwald ripening theories. The effect of preferred coalescence possibilities for definite particle size ranges and the effect of concurrent coalescence and Ostwald ripening are discussed.

  6. Synchronization of Coupled Reaction-Diffusion Neural Networks With Directed Topology via an Adaptive Approach.

    PubMed

    Zhang, Hao; Sheng, Yin; Zeng, Zhigang

    2017-03-15

    This paper investigates the synchronization issue of coupled reaction-diffusion neural networks with directed topology via an adaptive approach. Due to the complexity of the network structure and the presence of space variables, it is difficult to design proper adaptive strategies on coupling weights to accomplish the synchronous goal. Under the assumptions of two kinds of special network structures, that is, directed spanning path and directed spanning tree, some novel edge-based adaptive laws, which utilized the local information of node dynamics fully are designed on the coupling weights for reaching synchronization. By constructing appropriate energy function, and utilizing some analytical techniques, several sufficient conditions are given. Finally, some simulation examples are given to verify the effectiveness of the obtained theoretical results.

  7. Direct numerical simulation of shear localization and decomposition reactions in shock-loaded HMX crystal

    DOE PAGES

    Austin, Ryan A.; Barton, Nathan R.; Reaugh, John E.; ...

    2015-05-14

    A numerical model is developed to study the shock wave ignition of HMX crystal. The model accounts for the coupling between crystal thermal/mechanical responses and chemical reactions that are driven by the temperature field. This allows for the direct numerical simulation of decomposition reactions in the hot spots formed by shock/impact loading. The model is used to simulate intragranular pore collapse under shock wave loading. In a reference case: (i) shear-enabled micro-jetting is responsible for a modest extent of reaction in the pore collapse region, and (ii) shear banding is found to be an important mode of localization. The shearmore » bands, which are filled with molten HMX, grow out of the pore collapse region and serve as potential ignition sites. The model predictions of shear banding and reactivity are found to be quite sensitive to the respective flow strengths of the solid and liquid phases. In this regard, it is shown that reasonable assumptions of liquid-HMX viscosity can lead to chemical reactions within the shear bands on a nanosecond time scale.« less

  8. Direct numerical simulation of shear localization and decomposition reactions in shock-loaded HMX crystal

    SciTech Connect

    Austin, Ryan A.; Barton, Nathan R.; Reaugh, John E.; Fried, Laurence E.

    2015-05-14

    A numerical model is developed to study the shock wave ignition of HMX crystal. The model accounts for the coupling between crystal thermal/mechanical responses and chemical reactions that are driven by the temperature field. This allows for the direct numerical simulation of decomposition reactions in the hot spots formed by shock/impact loading. The model is used to simulate intragranular pore collapse under shock wave loading. In a reference case: (i) shear-enabled micro-jetting is responsible for a modest extent of reaction in the pore collapse region, and (ii) shear banding is found to be an important mode of localization. The shear bands, which are filled with molten HMX, grow out of the pore collapse region and serve as potential ignition sites. The model predictions of shear banding and reactivity are found to be quite sensitive to the respective flow strengths of the solid and liquid phases. In this regard, it is shown that reasonable assumptions of liquid-HMX viscosity can lead to chemical reactions within the shear bands on a nanosecond time scale.

  9. Coherent ultrafast lattice-directed reaction dynamics of triiodide anion photodissociation

    NASA Astrophysics Data System (ADS)

    Xian, Rui; Corthey, Gastón; Rogers, David M.; Morrison, Carole A.; Prokhorenko, Valentyn I.; Hayes, Stuart A.; Miller, R. J. Dwayne

    2017-06-01

    Solid-state reactions are influenced by the spatial arrangement of the reactants and the electrostatic environment of the lattice, which may enable lattice-directed chemical dynamics. Unlike the caging imposed by an inert matrix, an active lattice participates in the reaction, however, little evidence of such lattice participation has been gathered on ultrafast timescales due to the irreversibility of solid-state chemical systems. Here, by lowering the temperature to 80 K, we have been able to study the dissociative photochemistry of the triiodide anion (I3-) in single-crystal tetra-n-butylammonium triiodide using broadband transient absorption spectroscopy. We identified the coherently formed tetraiodide radical anion (I4•-) as a reaction intermediate. Its delayed appearance after that of the primary photoproduct, diiodide radical I2•-, indicates that I4•- was formed via a secondary reaction between a dissociated iodine radical (I•) and an adjacent I3-. This chemistry occurs as a result of the intermolecular interaction determined by the crystalline arrangement and is in stark contrast with previous solution studies.

  10. Coherent ultrafast lattice-directed reaction dynamics of triiodide anion photodissociation.

    PubMed

    Xian, Rui; Corthey, Gastón; Rogers, David M; Morrison, Carole A; Prokhorenko, Valentyn I; Hayes, Stuart A; Miller, R J Dwayne

    2017-06-01

    Solid-state reactions are influenced by the spatial arrangement of the reactants and the electrostatic environment of the lattice, which may enable lattice-directed chemical dynamics. Unlike the caging imposed by an inert matrix, an active lattice participates in the reaction, however, little evidence of such lattice participation has been gathered on ultrafast timescales due to the irreversibility of solid-state chemical systems. Here, by lowering the temperature to 80 K, we have been able to study the dissociative photochemistry of the triiodide anion (I3(-)) in single-crystal tetra-n-butylammonium triiodide using broadband transient absorption spectroscopy. We identified the coherently formed tetraiodide radical anion (I4(•)(-)) as a reaction intermediate. Its delayed appearance after that of the primary photoproduct, diiodide radical I2(•)(-), indicates that I4(•)(-) was formed via a secondary reaction between a dissociated iodine radical (I(•)) and an adjacent I3(-). This chemistry occurs as a result of the intermolecular interaction determined by the crystalline arrangement and is in stark contrast with previous solution studies.

  11. Zone sintering of ceramic fuels

    DOEpatents

    Matthews, R. Bruce; Chidester, Kenneth M.; Moore, H. Gene

    1994-01-01

    Cold pressed UC.sub.2 fuel compacts are sintered at temperatures greater than about 1850.degree. C. while in contact with a sintering facilitator material, e.g., tantalum, niobium, tungsten or a metal carbide such as uranium carbide, thereby allowing for a reduction in the overall porosity and leaving the desired product, i.e., a highly dense, large-grained uranium dicarbide. The process of using the sintering facilitator materials can be applied in the preparation of other carbide materials.

  12. Report on the sintering and properties of MgO and MgO-5% TiC

    SciTech Connect

    Bengisu, M.; Inal, O.T.

    1992-07-01

    Sintering of technical grade MgO yields higher fractional densities compared to pure MgO. TiC reacts with MgO under sintering of MgO-TiC composites in air, yielding Mg{sub 2}TiO{sub 4} and CO or CO{sub 2}. This can be suppressed in vacuum by plasma sintering. Plasma sintering of MgO at 1300 C and short times does not produce satisfactory results. 5 vol% TiC increases the sinterability of MgO during conventional air sintering; larger additions (50 vol%) decrease sinterability due to macropores formed by gaseous reaction product. Microwave sintering of MgO is possible. Mechanical properties of MgO are improved by additions of small amounts of TiC to starting powders.

  13. Direct Observation of Sulfur Radicals as Reaction Media in Lithium Sulfur Batteries

    SciTech Connect

    Wang, Qiang; Zheng, Jianming; Walter, Eric; Pan, Huilin; Lv, Dongping; Zuo, Pengjian; Chen, Honghao; Deng, Z. D.; Liaw, Bor Y.; Yu, Xiqian; Yang, Xiao-Qing; Zhang, Ji-Guang; Liu, Jun; Xiao, Jie

    2015-01-09

    Lithium sulfur (Li-S) battery has been regaining tremendous interest in recent years because of its attractive attributes such as high gravimetric energy, low cost and environmental benignity. However, it is still not conclusively known how polysulfide ring/chain participates in the whole cycling and whether the discharge and charge processes follow the same pathway. Herein, we demonstrate the direct observation of sulfur radicals by using in situ electron paramagnetic resonance (EPR) technique. Based on the concentration changes of sulfur radicals at different potentials and the electrochemical characteristics of the cell, it is revealed that the chemical and electrochemical reactions in Li-S cell are driving each other to proceed through sulfur radicals, leading to two completely different reaction pathways during discharge and charge. The proposed radical mechanism may provide new perspectives to investigate the interactions between sulfur species and the electrolyte, inspiring novel strategies to develop Li-S battery technology.

  14. Direct Observation of Sulfur Radicals as Reaction Media in Lithium Sulfur Batteries

    DOE PAGES

    Wang, Qiang; Zheng, Jianming; Walter, Eric; ...

    2015-01-09

    Lithium sulfur (Li-S) battery has been regaining tremendous interest in recent years because of its attractive attributes such as high gravimetric energy, low cost and environmental benignity. However, it is still not conclusively known how polysulfide ring/chain participates in the whole cycling and whether the discharge and charge processes follow the same pathway. Herein, we demonstrate the direct observation of sulfur radicals by using in situ electron paramagnetic resonance (EPR) technique. Based on the concentration changes of sulfur radicals at different potentials and the electrochemical characteristics of the cell, it is revealed that the chemical and electrochemical reactions in Li-Smore » cell are driving each other to proceed through sulfur radicals, leading to two completely different reaction pathways during discharge and charge. The proposed radical mechanism may provide new perspectives to investigate the interactions between sulfur species and the electrolyte, inspiring novel strategies to develop Li-S battery technology.« less

  15. Chemical Reactions and Mechanical Properties of the Directly Bonded Ge-Si Interface

    NASA Astrophysics Data System (ADS)

    Byun, Ki Yeol; Ferain, Isabelle; Yu, Ran; Colinge, Cindy

    2011-12-01

    In this study, chemical reactions and mechanical properties of directly bonded Ge-Si interfaces are investigated. The Ge-Si bonded interface has been systematically characterized as a function of the thermal budget (200 °C and 300 °C), which demonstrated that the formation of a thin GeO2 cap layer by radical pre-treatment can reduce the generation rate of voids at the bonded interface significantly. Patterning of one of the wafers prior to bonding can help to achieve high bonding quality thanks to enhanced out-diffusion of reaction by-products and stress reduction at the bonded interface. Both numerical modeling and structural analysis show that the presence of diffusion path (channels) at the bonded interfaces result in a maximum bond strength and minimum stress at the bonded interface.

  16. Direct Observation of Sulfur Radicals as Reaction Media in lithium Sulfur Batteries

    SciTech Connect

    Wang, Qiang; Zheng, Jianming; Walter, Eric D.; Pan, Huilin; Lu, Dongping; Zuo, Pengjian; Chen, Honghao; Deng, Zhiqun; Liaw, Bor Yann; Yu, Xiqian; Yang, Xiaoning; Zhang, Jiguang; Liu, Jun; Xiao, Jie

    2014-12-09

    Lithium sulfur (Li-S) battery has been regaining tremendous interest in recent years because of its attractive attributes such as high gravimetric energy, low cost and environmental benignity. However, it is still not conclusively known how polysulfide ring/chain participates in the whole cycling and whether the discharge and charge process follow the same pathway. Herein, we demonstrate the direct observation of sulfur radicals by using in situ electron paramagnetic resonance (EPR) technique. Based on the concentration changes of sulfur radicals at different potentials, it is revealed that the chemical and electrochemical reactions in Li-S cell are driven each other to proceed through sulfur radicals, leading to two completely different reaction pathways during discharge and charge. The proposed radical mechanism may provide new insights to investigate the interactions between sulfur species and the electrolyte, inspiring novel strategies to develop Li-S battery technology.

  17. Differences in posttraumatic stress reactions between witnesses and direct victims of motor vehicle accidents.

    PubMed

    Tierens, Marlies; Bal, Sarah; Crombez, Geert; Loeys, Tom; Antrop, Inge; Deboutte, Dirk

    2012-06-01

    The present study describes posttraumatic stress reactions in young witnesses of motor vehicle accidents (MVAs). This study investigated (a) whether witnesses of MVAs report fewer trauma symptoms than direct victims, but more than adolescents who were never exposed to an MVA; and (b) whether individual differences in sex, negative appraisal, avoidant coping, and social support account for variability in trauma symptoms beyond status as a witness as compared to a victim. Self-report data came from a community-based sample of 3,007 adolescents with an average age of 14.6 years and comprising 53% boys. Compared to direct victims of an MVA in which someone was injured, witnesses of MVAs with injury reported significantly less internalizing symptoms, such as symptoms of posttraumatic stress (d = 0.25), fear (d = 0.21), and depression (d = 0.17). Compared to adolescents who were never exposed to an MVA with injury, witnesses reported significantly more externalizing symptoms (d = 0.24). In multiple regression analyses the significant difference between witnesses and victims disappeared when sex, other stressful events, appraisals, and coping were added to the model. These findings suggest that adolescent witnesses, as well as direct victims, may be at risk for posttraumatic reactions. Copyright © 2012 International Society for Traumatic Stress Studies.

  18. Biomimetic versus Sintered Calcium Phosphates: The in vitro Behavior of Osteoblasts and Mesenchymal Stem Cells.

    PubMed

    Sadowska, Joanna Maria; Guillem-Marti, Jordi; Montufar, Edgar B; Espanol, Montserrat; Ginebra, Maria-Pau

    2017-01-20

    The fabrication of calcium phosphates using biomimetic routes, namely, precipitation processes at body temperature, results in distinct features compared to conventional sintered calcium phosphate ceramics, such as a high specific surface area and micro or nanometric crystal size. The aim of this paper is to analyze the effects of these parameters on cell response, focusing on two bone cell types: rat mesenchymal stem cells (rMSCs) and human osteoblastic cells (SaOS-2). Biomimetic calcium deficient hydroxyapatite (CDHA) was obtained by a low temperature setting reaction, and α-tricalcium phosphate (α-TCP) and β- tricalcium phosphate (β-TCP) were subsequently obtained by sintering CDHA either at 1400 °C or 1100 °C. Sintered stoichiometric hydroxyapatite (HA) was also prepared using ceramic routes. The materials were characterized in terms of specific surface area, skeletal density, porosity and pore size distribution. SaOS-2 cells and rMSCs were seeded either directly on the surfaces of the materials or on glass coverslips subsequently placed on top of the materials to expose the cells to the CaP-induced ionic changes in the culture medium while avoiding any topography-related effects. CDHA produced higher ionic fluctuations in both cell culture media than sintered ceramics, with a strong decrease of calcium and a release of phosphate. Indirect contact cell cultures revealed that both cell types were sensitive to these ionic modifications, resulting in a decrease in proliferation rate, more marked for CDHA, this effect being more pronounced for rMSCs. In direct contact cultures, good cell adhesion was found on all materials, but whereas cells were able to proliferate on the sintered calcium phosphates, cell number was significantly reduced with time on biomimetic CDHA, which was associated to a higher percentage of apoptotic cells. Direct contact of the cells with biomimetic CDHA resulted also in higher ALP activity for both cell types as compared to sintered

  19. Thermoluminescence properties of sintered ZnO

    NASA Astrophysics Data System (ADS)

    Borbón-Nuñez, H. A.; Cruz-Vázquez, C.; Bernal, R.; Kitis, G.; Furetta, C.; Castaño, V. M.

    2014-11-01

    New pellet-shaped ZnO phosphors were synthesized using a controlled chemical reaction. Some samples were sintered at 1123, 1173 or 1223 K during 24 h in air, and then exposed to beta particle irradiation in the dose range from 25 to 800 Gy to investigate their thermoluminescence (TL) properties. By considering their sensitivity, reproducibility, and fading features, samples sintered at 1173 K exhibit the best dosimetric characteristics. From computerized glow curve deconvolution that was carried out using a general order equation, the kinetics parameters were computed, and it was found that the glow curves are composed by six individual TL peaks with kinetics order ranging from 1.2 to 1.8.

  20. Production of sintered porous metal fluoride pellets

    DOEpatents

    Anderson, L.W.; Stephenson, M.J.

    1973-12-25

    Porous pellets characterized by a moderately reactive crust and a softer core of higher reactivity are produced by forming agglomerates containing a metal fluoride powder and a selected amount ofwater. The metal fluoride is selected to be sinterable and essentially non-reactive with gaseous fluorinating agents. The agglomerates are contacted with a gaseous fluorinating agent under controlled conditions whereby the heat generated by localized reaction of the agent and water is limited to values effccting bonding by localized sintering. Porous pellets composed of cryolite (Na/sub 3/AlF/sub 6/) can be used to selectively remove trace quantities of niobium pentafluoride from a feed gas consisting predominantly of uranium hexafluoride. (Official Gazette)

  1. Activated sintering of zirconium dioxide

    NASA Astrophysics Data System (ADS)

    Panin, V. E.; Slosman, A. I.; Matrenin, S. V.

    1996-02-01

    A new phenomenon has been observed — the activated sintering of a zirconium ceramic in the hydrogen-nitrogen plasma of a glow discharge. It is shown that the activation energy is considerably lower than the activation energy for sintering in a vacuum furnace. This makes it possible to reduce sintering temperature, refine the grains, and improve the mechanical properties of the ceramic. It is proposed that the mechanism by which sintering is activated is connected with the activating effect of hydrogen during a structural transformation involving the formation of oxynitride phases.

  2. Spark plasma sintering of titanium aluminide intermetallics and its composites

    NASA Astrophysics Data System (ADS)

    Aldoshan, Abdelhakim Ahmed

    Titanium aluminide intermetallics are a distinct class of engineering materials having unique properties over conventional titanium alloys. gamma-TiAl compound possesses competitive physical and mechanical properties at elevated temperature applications compared to Ni-based superalloys. gamma-TiAl composite materials exhibit high melting point, low density, high strength and excellent corrosion resistance. Spark plasma sintering (SPS) is one of the powder metallurgy techniques where powder mixture undergoes simultaneous application of uniaxial pressure and pulsed direct current. Unlike other sintering techniques such as hot iso-static pressing and hot pressing, SPS compacts the materials in shorter time (< 10 min) with a lower temperature and leads to highly dense products. Reactive synthesis of titanium aluminide intermetallics is carried out using SPS. Reactive sintering takes place between liquid aluminum and solid titanium. In this work, reactive sintering through SPS was used to fabricate fully densified gamma-TiAl and titanium aluminide composites starting from elemental powders at different sintering temperatures. It was observed that sintering temperature played significant role in the densification of titanium aluminide composites. gamma-TiAl was the predominate phase at different temperatures. The effect of increasing sintering temperature on microhardness, microstructure, yield strength and wear behavior of titanium aluminide was studied. Addition of graphene nanoplatelets to titanium aluminide matrix resulted in change in microhardness. In Ti-Al-graphene composites, a noticeable decrease in coefficient of friction was observed due to the influence of self-lubrication caused by graphene.

  3. Sinter-forging of nanophase TiO sub 2

    SciTech Connect

    Uchic, M.; Hofler, H.J.; Flick, W.J.; Tao, R.; Averback, R.S. . Dept. of Materials Science and Engineering); Kurath, P. . Dept. of Mechanical Engineering)

    1992-03-01

    Considerable effort has been directed in recent years to developing ceramic materials that can be both sintered to full density at low temperatures and processed by superplastic forming. One strategy for achieving this goal has been to reduce the particle size of the starting powder, and by anaphase processing, particles of sizes less than {approx}10 nm can now be realized. Indeed, recent studies on nanophase ceramics have demonstrated that sintering temperatures can be reduced dramatically and that nanophase ceramics have excellent potential for superplastic forming. Nevertheless, the grain growth that occurs during the processing of these new materials restricts their applicability. In nanophase (n-) TiO{sub 2}, some progress in controlling grain size has been achieved by using dopants or hot pressing. Sinter-forging offers another means to achieve this goal, although this method has been applied mostly to materials with larger grains. Studies of sinter-forging are also useful for elucidating the mechanisms of sintering and creep in ceramic materials. In the present paper, the authors examine the characteristics of sinter-forging in n-TiO{sub 2}. Only limited studies of sinter-forging have thus far been performed on well characterized powders of comparable size, and even these had a somewhat larger grain size.

  4. Direct Assembly of Prenylated Heteroarenes through a Cascade Minisci Reaction/Dehydration Sequence

    PubMed Central

    Tan, Dong‐Hang; Zeng, Yao‐Fu; Liu, Yao; Lv, Wen‐Xin; Li, Qingjiang

    2016-01-01

    Abstract The prenyl group is an important component in bioactive compounds. Herein, we report the assembly of prenylated heteroarenes through a cascade Minisci reaction and acid‐promoted dehydration sequence. The use of potassium (3‐hydroxy‐3‐methylbut‐1‐yl)trifluoroborate as a new coupling reagent allows the direct introduction of prenyl and 3‐hydroxy‐3‐methylbutyl groups to a wide variety of electron‐deficient heteroarenes. Synthetic application is also demonstrated. PMID:28032022

  5. Sinterable Powders from Laser Driven Reactions

    DTIC Science & Technology

    1980-07-01

    151.5 Ether 19 Isopentyl Ether 2.82 a 22.9 a 173.2 Aliphatic Acids 20 Propionic Acid 3.30 e 26.7 a 141.0 1.10 a 21 Butyric Acid 2.97 a 26.5 a 163.5 1.54...A 0 17 2-Pent anone A 00 18 2-Heptanone A O Ether 19 Isopentyl Ether B* Aliphatic Acids 20 Propionic Acid B 0 21 Butyric Acid B* Aldehydes 22...Not Measured 60 with a very low dielectric constants such as n-hexane, cyclohexane, n-octane, benzene, toluene, xylene, isopentyl ether, propionic

  6. Direct nuclear-pumped lasers using the He-3/n,p/H-3 reaction

    NASA Technical Reports Server (NTRS)

    Deyoung, R. J.; Jalufka, N. W.; Hohl, F.

    1978-01-01

    A description is presented of experimental results concerning a specific class of direct nuclear-pumped lasers classified as 'volumetric nuclear lasers'. In the considered laser system a fissioning gas, He-3, is mixed with the lasing gas to form a homogeneous mixture, resulting in uniform volume excitation. In typical volumetric nuclear lasers a fast-burst reactor is used as a source of neutrons which penetrate a polyethylene moderator. Here the fast neutrons are thermalized. After thermalization, neutrons scatter into the laser cell. Nuclear reactions produce a proton of 0.56 MeV and a tritium ion of 0.19. These ions produce secondary electrons which pump the laser medium creating a population inversion. The results reported demonstrate direct nuclear pumping of He-3-Ar, Xe, Kr, and Cl with the considered system.

  7. Directed surfaces structures and interfaces for enhanced electrocatalyst activity, selectivity, and stability for energy conversion reactions

    SciTech Connect

    Jaramillo, Thomas F.

    2016-04-20

    In this project, we have employed a systematic approach to develop active, selective, and stable catalyst materials for important electrochemical reactions involving energy conversion. In particular, we have focused our attention on developing active catalyst materials for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). HER: We have synthesized and investigated several highly active and acid stable non-precious metal HER catalysts, including: [Mo3S13]2- nanoclusters (Nature Chemistry, 2014) and molybdenum phosphosulfide (MoP|S) (Angewandte Chemie, 2014). We have also aimed to engineer these catalyst formulations in a membrane electrode assembly (MEA) for fundamental studies of water electrolysis at high current densities, approximately 1 A/cm2 (ChemSusChem, 2015). We furthermore investigated transition metal phosphide (TMP) catalysts for HER by a combined experimental–theoretical approach (Energy & Environmental Science, 2015). By synthesizing different TMPs and comparing experimentally determined HER activities with the hydrogen adsorption free energies, ΔGH, calculated by density functional theory, we showed that the TMPs follow a volcano relationship for the HER. Using our combined experimental–theoretical model, we predicted that the mixed metal TMP, Fe0.5Co0.5P, should have a near-optimal ΔGH. We synthesized several mixtures of Co and Fe phosphides alloys and confirmed that Fe0.5Co0.5P exhibits the highest HER activity of the investigated TMPs (Energy & Environmental Science, 2015). The understanding gained as to how to improve catalytic activity for the HER, particularly for non-precious metal materials, is important to DOE targets for sustainable H2 production. OER: We have developed a SrIrO3/IrOx catalyst for acidic conditions (submitted, 2016). The Sr

  8. Flash sintering of ceramic materials

    NASA Astrophysics Data System (ADS)

    Dancer, C. E. J.

    2016-10-01

    During flash sintering, ceramic materials can sinter to high density in a matter of seconds while subjected to electric field and elevated temperature. This process, which occurs at lower furnace temperatures and in shorter times than both conventional ceramic sintering and field-assisted methods such as spark plasma sintering, has the potential to radically reduce the power consumption required for the densification of ceramic materials. This paper reviews the experimental work on flash sintering methods carried out to date, and compares the properties of the materials obtained to those produced by conventional sintering. The flash sintering process is described for oxides of zirconium, yttrium, aluminium, tin, zinc, and titanium; silicon and boron carbide, zirconium diboride, materials for solid oxide fuel applications, ferroelectric materials, and composite materials. While experimental observations have been made on a wide range of materials, understanding of the underlying mechanisms responsible for the onset and latter stages of flash sintering is still elusive. Elements of the proposed theories to explain the observed behaviour include extensive Joule heating throughout the material causing thermal runaway, arrested by the current limitation in the power supply, and the formation of defect avalanches which rapidly and dramatically increase the sample conductivity. Undoubtedly, the flash sintering process is affected by the electric field strength, furnace temperature and current density limit, but also by microstructural features such as the presence of second phase particles or dopants and the particle size in the starting material. While further experimental work and modelling is still required to attain a full understanding capable of predicting the success of the flash sintering process in different materials, the technique non-etheless holds great potential for exceptional control of the ceramic sintering process.

  9. Direct kinetic measurements of reactions between the simplest Criegee intermediate CH2OO and alkenes.

    PubMed

    Buras, Zachary J; Elsamra, Rehab M I; Jalan, Amrit; Middaugh, Joshua E; Green, William H

    2014-03-20

    The simplest Criegee Intermediate (CH2OO), a well-known biradical formed in alkene ozonolysis, is known to add across double bonds. Here we report direct experimental rate measurements of the simplest Criegee Intermediate reacting with C2–C4 alkenes obtained using the laser flash photolysis technique probing the recently measured B(1)A′ ← X(1)A′ transition in CH2OO. The measured activation energy (298–494 K) for CH2OO + alkenes is Ea ≈ 3500 ± 1000 J mol(–1) for all alkyl substituted alkenes and Ea = 7000 ± 900 J mol(–1) for ethene. The measured Arrhenius pre-exponential factors (A) vary between (2 ± 1) × 10(–15) and (11 ± 3) × 10(–15) cm(3) molecule(–1) s(–1). Quantum chemical calculations of the corresponding rate coefficients reproduce qualitative reactivity trends but overestimate the absolute rate coefficients. Despite the small Ea's, the CH2OO + alkene rate coefficients are almost 2 orders of magnitude smaller than those of similar reactions between CH2OO and carbonyl compounds. Using the rate constants measured here, we estimate that, under typical atmospheric conditions, reaction with alkenes does not represent a significant sink of CH2OO. In environments rich in C═C double bonds, however, such as ozone-exposed rubber or emission plumes, these reactions can play a significant role.

  10. Direct visualization of a cycloaddition reaction on frozen asymmetric Si dimers at room temperature

    NASA Astrophysics Data System (ADS)

    Baik, Jaeyoon; Ihm, Kyuwook; Ha, Taekyun; An, Ki-Seok; Ahn, Joung Real; Park, Chong-Yun

    2016-07-01

    We firstly report an experimental visualization of a cycloaddition reaction on RT frozen asymmetric Si dimers. The frozen Si dimers with a local c(4 × 2) order were prepared by pinning flip-flopping Si dimers by using molecules. This RT pristine c(4 × 2) structure was used to determine what Si atom of an asymmetric Si dimer bonds to a molecule at the initial stage of the RT cycloaddition reaction, which has been a long-standing puzzling issue. This made it possible to compare directly experimental cycloaddition reactions with theoretical ones. As a prototype for the experiment, a 1,3-butadiene molecule adsorbed between Si dimer rows was used. The 1,3-butadiene molecule was found to prefer a symmetric Si pair on the frozen Si dimers, i.e., two electrophilic lower atoms of asymmetric Si dimers. This result is consistent with the theoretical prediction that a 1,3-diene molecule prefers a symmetric Si pair on the Si(001)c(4 × 2) surface. This experimental approach can also be applied to other studies for the adsorption of a molecule on a Si(001) surface at room temperature.

  11. Probable new type of reaction mechanism: Double. cap alpha. direct transfer process

    SciTech Connect

    Xu Shu-wei; Wu Guo-hua; Miao Rong-zhi; Han Fei

    1983-10-01

    It is assumed that /sup 8/Be consists of two ..cap alpha.. particles which are close to each other in configuration space. A spectroscopic density of /sup 8/Be cluster in the residue nuclei is then obtained, which is proportional to the square of the preformation probability of ..cap alpha.. particle at nuclear surface. Using the improved method of parametrization of EFR-DWBA overlap integral,/sup 1//sup en-dash//sup 2/ we calculate the double differential energy spectra and angular distributions of ..cap alpha.. particles for the reactions /sup 209/Bi (/sup 12/C, ..cap alpha..) /sup 217/Fr and extract the preformation probability of ..cap alpha.. particle at the surface of /sup 217/Fr nuclei from fitting the experimental data. The agreement within the range of calculation error between the preformation probabilities extracted from transfer reactions and ..cap alpha.. decay suggests that the reaction /sup 209/Bi(/sup 12/C, ..cap alpha..) /sup 217/Fr may be explained as a double ..cap alpha.. direct transfer process.

  12. Electrified emotions: Modulatory effects of transcranial direct stimulation on negative emotional reactions to social exclusion.

    PubMed

    Riva, Paolo; Romero Lauro, Leonor J; Vergallito, Alessandra; DeWall, C Nathan; Bushman, Brad J

    2015-01-01

    Social exclusion, ostracism, and rejection can be emotionally painful because they thwart the need to belong. Building on studies suggesting that the right ventrolateral prefrontal cortex (rVLPFC) is associated with regulation of negative emotions, the present experiment tests the hypothesis that decreasing the cortical excitability of the rVLPFC may increase negative emotional reactions to social exclusion. Specifically, we applied cathodal transcranial direct current stimulation (tDCS) over the rVLPFC and predicted an increment of negative emotional reactions to social exclusion. In Study 1, participants were either socially excluded or included, while cathodal tDCS or sham stimulation was applied over the rVLPFC. Cathodal stimulation of rVLPFC boosted the typical negative emotional reaction caused by social exclusion. No effects emerged from participants in the inclusion condition. To test the specificity of tDCS effects over rVLPFC, in Study 2, participants were socially excluded and received cathodal tDCS or sham stimulation over a control region (i.e., the right posterior parietal cortex). No effects of tDCS stimulation were found. Our results showed that the rVLPFC is specifically involved in emotion regulation and suggest that cathodal stimulation can increase negative emotional responses to social exclusion.

  13. Direct determination of reaction paths and stationary points on potential of mean force surfaces.

    PubMed

    Li, Guohui; Cui, Qiang

    2005-10-01

    A simulation approach is introduced for directly determining reaction paths and stationary points on potential of mean force (PMF) surfaces associated with molecular events that occur in complex environments. The nudged elastic band approach was employed to search for steepest descent paths on the PMF surface using the relevant PMF derivatives from a series of local simulations. The steepest descent path on the PMF surface corresponds to the minimum PMF path (i.e. the path with the lowest local PMF barrier), which contains important information about stationary points (e.g. saddle points) on the PMF surface, which in turn can provide useful insights into the thermodynamics and kinetics for the process of interest. By working with the PMF defined in a low-dimensional sub-space rather than a potential energy function of full molecular dimensionality, the main features of the process under study are concisely represented and the orthogonal degrees of freedom are adequately sampled with the appropriate canonical distribution at the desired temperature (e.g. 300 K). Therefore, minimum PMF paths carry statistically meaningful mechanistic information and are complementary to reaction paths of full molecular dimensionality proposed in previous studies. The NEB based path optimization method is direct in the sense that no information regarding the global PMF surface is necessary for the determination of the local reaction path and stationary points along this path. Since only low-dimensional quantities (paths) are searched for, the PMF-path method is expected to scale better in terms of dimension of the PMF sub-space than those aims to fully explore multi-dimensional PMF surfaces. Test applications on simple molecular systems, the alanine di-peptide in vacuum and in solution and a micro-solvated proton-wire, indicate that reliable PMF paths can be determined for both conformational isomerization and chemical reaction processes. However, highly accurate PMF derivatives are

  14. Stereodynamics of the F + HD(v = 0, j = 1) reaction: direct vs. resonant mechanisms.

    PubMed

    Aldegunde, Jesús; Jambrina, Pablo G; de Miranda, Marcelo P; Sáez Rábanos, Vicente; Aoiz, F Javier

    2011-05-14

    The stereodynamics and mechanism of the F + HD(v = 0, j = 1) → HF (DF) + D (H) reactions have been thoroughly analysed at collision energies in the 0-160 meV range. Specifically, this study is focused on (i) the comparison between the stereodynamics of the collisions leading to HF and DF formation, and (ii) the stereodynamical fingerprints of the resonance that occurs at low collision energies in the HF channel and whose manifestation in the total cross section is greatly diminished for initial j > 0. While previous studies were limited to the analysis of integral cross sections (ICS), differential cross sections (DCS) and reaction probabilities, in the present work we have included the analysis of vectorial quantities such as the direction of the initial rotational angular momentum and internuclear axis, and their effect on reactivity. In particular, polarisation parameters (PP) and polarisation dependent differential cross sections (PDDCS), quantities that describe how the intrinsic HD rotational angular momentum and molecular axis polarisations contribute to reaction, are calculated and examined. The evolution of the PPs with the collision energy differs markedly between the two reaction channels. For the DF channel, the PP values are small and change very little in the energy range in which DF formation is appreciable. In contrast, rapid fluctuations in the magnitude and sign of the PPs are observed in the HF channel at low collision energies in and around the resonance. As the collision energy increases, direct (non-resonant) scattering prevails, and the various quantities are reasonably well accounted for by the QCT calculations, as in the case of the DF channel. The intrinsic directional information has been used to access the extent of control that can be achieved through polarisation of the HD molecule prior to collision. It was found that the same extrinsic preparation leads to very different outcomes on the HF channel DCS when the collision energy is

  15. Ultrafast electron diffraction and direct observation of transient structures in a chemical reaction

    PubMed Central

    Cao, Jianming; Ihee, Hyotcherl; Zewail, Ahmed H.

    1999-01-01

    Ultrafast electron diffraction is a unique method for the studies of structural changes of complex molecular systems. In this contribution, we report direct ultrafast electron diffraction study of the evolution of short-lived intermediates in the course of a chemical change. Specifically, we observe the transient intermediate in the elimination reaction of 1,2-diiodotetrafluoroethane (C2F4I2) to produce the corresponding ethylene derivative by the breakage of two carbon–iodine, C—I, bonds. The evolution of the ground-state intermediate (C2F4I radical) is directly revealed in the population change of a single chemical bond, namely the second C—I bond. The elimination of two iodine atoms was shown to be nonconcerted, with reaction time of the second C—I bond breakage being 17 ± 2 ps. The structure of the short-lived C2F4I radical is more favorable to the classical radical structure than to the bridged radical structure. This leap in our ability to record structural changes on the ps and shorter time scales bodes well for many future applications in complex molecular systems. PMID:9892634

  16. Different Relative Orientation of Static and Alternative Magnetic Fields and Cress Roots Direction of Growth Changes Their Gravitropic Reaction

    NASA Astrophysics Data System (ADS)

    Sheykina, Nadiia; Bogatina, Nina

    The following variants of roots location relatively to static and alternative components of magnetic field were studied. At first variant the static magnetic field was directed parallel to the gravitation vector, the alternative magnetic field was directed perpendicular to static one; roots were directed perpendicular to both two fields’ components and gravitation vector. At the variant the negative gravitropysm for cress roots was observed. At second variant the static magnetic field was directed parallel to the gravitation vector, the alternative magnetic field was directed perpendicular to static one; roots were directed parallel to alternative magnetic field. At third variant the alternative magnetic field was directed parallel to the gravitation vector, the static magnetic field was directed perpendicular to the gravitation vector, roots were directed perpendicular to both two fields components and gravitation vector; At forth variant the alternative magnetic field was directed parallel to the gravitation vector, the static magnetic field was directed perpendicular to the gravitation vector, roots were directed parallel to static magnetic field. In all cases studied the alternative magnetic field frequency was equal to Ca ions cyclotron frequency. In 2, 3 and 4 variants gravitropism was positive. But the gravitropic reaction speeds were different. In second and forth variants the gravitropic reaction speed in error limits coincided with the gravitropic reaction speed under Earth’s conditions. At third variant the gravitropic reaction speed was slowed essentially.

  17. Studies on exotic nuclei by proton-induced direct reaction at GSI and FAIR

    SciTech Connect

    Kiselev, O. A.

    2007-02-26

    The proton-induced direct reactions like elastic, quasi-elastic scattering and knock-out at intermediate energies and inverse kinematics are the most powerful classical methods for obtaining spectroscopic information on the structure of unstable exotic nuclei. Few elastic scattering experiments performed at GSI with the gaseous and liquid hydrogen targets provided the most precise data on a nuclear matter distribution and a halo-core structure of the neutron-rich He and Li isotopes. The measured differential cross sections have been also used for probing density distributions as predicted by various microscopic theories. The comparison of the data with the latest calculations will be shown. The description of the recent experiment with proton-rich 8B and neutron-rich Be isotopes is presented.The experimental conditions at the future facility FAIR will provide unique opportunities for nuclear structure studies on nuclei far off stability, and will allow to reach new regions in the chart of nuclides of high interest for nuclear structure and astrophysics. In particular, predicted luminosity will allow for the investigation of direct reactions with stored and cooled radioactive beams at internal H, He, etc. targets of the storage ring NESR. This technique enables high resolution measurements down to very low momentum transfer and provides a gain in luminosity from accumulation and recirculation of the radioactive beams. In order to explore the experimental conditions for measurements planned at EXL/FAIR setup, a first attempt exploring experimentally the feasibility of its concept has been recently made. A detector setup was installed at the ESR storage ring at GSI, Darmstadt. A 136Xe beam was interacting to an internal hydrogen gas-jet target. The detector setup had all the basic ingredients as foreseen by EXL collaboration. A set of scattering reactions has been studied and the overall performance of the setup demonstrated the feasibility of the EXL experimental

  18. Characterization of spark plasma sintered Ag nanopowders.

    PubMed

    Fu, Y Q; Shearwood, C; Xu, B; Yu, L G; Khor, K A

    2010-03-19

    The low temperature sintering behaviour of nanocrystalline Ag powder (with an average size of 70 nm) was characterized. Using spark plasma sintering (SPS), the Ag nanopowders can be successfully sintered at low pressure for only 5 min without external heating, and the sintering density increases and porosity decreases significantly with increase in the sintering temperature. Nanoindentation has been used to characterize the SPS sintered Ag samples. The mechanisms of the low sintering temperature behaviour of the nano-Ag powder and the nanoscale mechanical performance have been discussed. Compression tests were also used to characterize the mechanical properties of the sintered Ag sample with a maximum strain up to 15%.

  19. Effect of milling and leaching on the structure of sintered silicon

    NASA Technical Reports Server (NTRS)

    Yeh, H. C.; Glasgow, T. K.; Herbell, T. P.

    1980-01-01

    The effects of attrition milling and acid leaching on the sintering behavior and the resultant structures of two commercial silicon powders were investigated. Sintering was performed in He for 16 hours at 1200, 1250, and 1300 C. Compacts of as-received Si did not densify during sintering. Milling reduced the average particle size to below 0.5 microns and enhanced densification (1.75 g/cc). Leaching milled Si further enhanced densification (1.90 g/cc max.) and decreased structural coarsening. After sintering, the structure of the milled and leached powder compacts appears favorable for the production of reaction bonded silicon nitride.

  20. Microwave sintering of multiple articles

    DOEpatents

    Blake, Rodger D.; Katz, Joel D.

    1993-01-01

    Apparatus and method for producing articles of alumina and of alumina and silicon carbide in which the articles are sintered at high temperatures using microwave radiation. The articles are placed in a sintering container which is placed in a microwave cavity for heating. The rates at which heating and cooling take place is controlled.

  1. A research on sintering characteristics and mechanisms of dried sewage sludge.

    PubMed

    Wang, Xingrun; Jin, Yiying; Wang, Zhingyu; Mahar, Rasool Bux; Nie, Yongfeng

    2008-12-30

    This study investigates the sintering behavior of dried sewage sludge and the related sintering mechanisms, considering sintering temperature and sintering time. Experimental results indicate that the characteristics are primarily influenced by sintering temperature. When the sintering temperature is increased from 1020 to 1050 degrees C, the specimens' compressive strength and bulk density increase significantly, while water absorption decreases obviously, indicating an improvement of densification due to sintering. However, the compressive strength cannot meet the requirement for traditional ceramic products due to the release of organic matters and the formation of big pores in the products. Phosphorus in sewage sludge initially takes reactions with the formation of calcium magnesium phosphate and aluminum phosphate during sintering, which are helpful for enhancing the compressive strength. So, some materials with high contents of Al could be used to enhance the compressive strength of products. Heavy metals are fixed primarily inside the sintered specimens, with the As, Pb, Cd, Cr, Ni, Cu, Zn concentrations in the leachate found to be in the range of China regulatory requirements. These results reveal the feasibility of recycling dried sewage sludge by sintering as a construction material.

  2. A macroscopic reaction: direct covalent bond formation between materials using a Suzuki-Miyaura cross-coupling reaction.

    PubMed

    Sekine, Tomoko; Kakuta, Takahiro; Nakamura, Takashi; Kobayashi, Yuichiro; Takashima, Yoshinori; Harada, Akira

    2014-09-18

    Cross-coupling reactions are important to form C-C covalent bonds using metal catalysts. Although many different cross-coupling reactions have been developed and applied to synthesize complex molecules or polymers (macromolecules), if cross-coupling reactions are realized in the macroscopic real world, the scope of materials should be dramatically broadened. Here, Suzuki-Miyaura coupling reactions are realized between macroscopic objects. When acrylamide gel modified with an iodophenyl group (I-gel) reacts with a gel possessing a phenylboronic group (PB-gel) using a palladium catalyst, the gels bond to form a single object. This concept can also be adapted for bonding between soft and hard materials. I-gel or PB-gel selectively bonds to the glass substrates whose surfaces are modified with an electrophile or nucleophile, respectively.

  3. Manufacture of sintered silicon nitrides

    NASA Technical Reports Server (NTRS)

    Iwai, T.

    1985-01-01

    Sintered silicon nitrides are manufactured by sintering Si3N powder containing 2 to 15% in wt of a powder mixture composed of nitride powder of lanthanide or Y 100 parts and AIN powder less than 100 parts at 1500 to 1900 deg. temperature under a pressure of less than 200 Kg/sq. cm. The sintered Si3N has high mechanical strength in high temperature. Thus, Si3N4 93.0, Y 5.0 and AlN 2.0% in weight were wet mixed in acetone in N atom, molded and sintered at 1750 deg. and 1000 Kg/sq. cm. to give a sintered body having high hardness.

  4. Laser sintering of copper nanoparticles

    NASA Astrophysics Data System (ADS)

    Zenou, Michael; Ermak, Oleg; Saar, Amir; Kotler, Zvi

    2014-01-01

    Copper nanoparticle (NP) inks serve as an attractive potential replacement to silver NP inks in functional printing applications. However their tendency to rapidly oxidize has so far limited their wider use. In this work we have studied the conditions for laser sintering of Cu-NP inks in ambient conditions while avoiding oxidation. We have determined the regime for stable, low-resistivity copper (< ×3 bulk resistivity value) generation in terms of laser irradiance and exposure duration and have indicated the limits on fast processing. The role of pre-drying conditions on sintering outcome has also been studied. A method, based on spectral reflectivity measurements, was used for non-contact monitoring of the sintering process evolution. It also indicates preferred spectral regions for sintering. Finally, we illustrated how selective laser sintering can generate high-quality, fine line (<5 µm wide) and dense copper circuits.

  5. Novel bulk carbon nanotube materials for implant by spark plasma sintering.

    PubMed

    Wang, Wei; Omori, Mamoru; Watari, Fumio; Yokoyama, Atsuro

    2005-12-01

    Novel, bulk multiwall carbon nanotubes (MWCNTs) sintered with polycarbosilane (PCS) as a binder agent were fabricated by spark plasma sintering (SPS), and their microstructure and properties were investigated. Sintering was done with 20-60 MPa pressure at 1200 degrees C. SEM and TEM observations showed that the nanosized tube microstructure was preserved even after sintering, and tubes adhered to each other with the nanosized nodules of SiC pyrolyzed form PCS as revealed by X-ray diffraction. Bulk density and Vickers hardness were found to increase, whereas the specific surface area decreased, as PCS content and sintering pressure increased. Through animal experiments, the inflammatory reaction of CNTs/PCS material was found to be slightly increased with increasing PCS content. In conclusion, sintered CNTs had physical and mechanical properties close to bone, and their good biocompatibility based on tissue response served to pave their way as a suitable implant material in the future.

  6. Processing of bulk Al7075 alloy by spark plasma sintering

    NASA Astrophysics Data System (ADS)

    Málek, P.; Molnárová, O.; Cinert, J.; Lukáč, F.; Chráska, T.

    2017-02-01

    The main advantages of powder metallurgy processing route are the possibility to produce near-net-shape compacts and to minimize the finish machining and material loss. The main problem in particle consolidation process is to suppress porosity, to remove oxide layers, and to retain the microstructure of powder materials. Spark plasma sintering (SPS) combines concurrent uniaxial pressure and direct heating by a pulsed DC current. Sintering occurs at relatively low temperatures for a short time and does not influence significantly the microstructure in the interiors of original powder particles. The efficiency of SPS in producing compacts with low porosity might be dependent on the distribution of particle size in original powder material. The gas atomized Al7075 powder was sieved to several charges and then sintered by SPS. Microstructure of sintered compacts was studied by light and scanning electron microscopy. The phase composition was investigated using X-ray diffraction. The mechanical behaviour was tested by bending tests.

  7. Direct access to ketones from aldehydes via rhodium-catalyzed cross-coupling reaction with potassium trifluoro(organo)borates.

    PubMed

    Pucheault, Mathieu; Darses, Sylvain; Genet, Jean-Pierre

    2004-12-01

    A direct cross-coupling reaction of aromatic aldehydes with potassium trifluoro(organo)borates afforded ketones in high yields and under mild conditions in the presence of a rhodium catalyst and acetone. This new reaction, involving a formal aldehyde C-H bond activation, is believed to proceed via a Heck-type mechanism followed by hydride transfer to acetone.

  8. Enantioselective direct Mannich reactions of cyclic β-ketoesters catalyzed by chiral phosphine via a novel dual-reagent catalysis.

    PubMed

    Lou, Yan-Peng; Zheng, Chang-Wu; Pan, Ren-Ming; Jin, Qiao-Wen; Zhao, Gang; Li, Zhong

    2015-02-06

    A combination of an amino acid derived chiral phosphine catalyst and methyl acrylate efficiently catalyzed the direct Mannich reaction of cyclic β-ketoesters and N-Boc-aldimines. The dual-reagent catalysis was presumed to function through the formation of a zwitterion, which catalyzed the reaction with excellent stereocontrol via a hydrogen-bonding assisted chiral ion-pair pathway.

  9. Sintered silicon nitrode recuperator fabrication

    NASA Technical Reports Server (NTRS)

    Gatti, A.; Chiu, W. S.; Mccreight, L. R.

    1980-01-01

    The preliminary design and a demonstration of the feasibility of fabricating submodules of an automotive Stirling engine recuperator for waste heat recovery at 370 C are described. Sinterable silicon nitride (Sialon) tubing and plates were fabricated by extrusion and hydrostatic pressing, respectively, suitable for demonstrating a potential method of constructing ceramic recuperator-type heat exchangers. These components were fired in nitrogen atmosphere to 1800 C without significant scale formation so that they can be used in the as-fired condition. A refractory glass composition (Al2O3 x 4.5 CaO.MgO x 11SiO2) was used to join and seal component parts by a brazing technique which formed strong recuperator submodules capable of withstanding repeated thermal cycling to 1370 C. The corrosion resistance of these materials to Na2SO4 + NaCl carbon mixtures was also assessed in atmospheres of air, hydrogen and CO2-N2-H2O mixtures at both 870 C and 1370 C for times to 1000 hours. No significant reaction was observed under any of these test conditions.

  10. Detection of Mycoplasma Contamination Directly from Culture Supernatant Using Polymerase Chain Reaction.

    PubMed

    Pisal, R V; Hrebíková, H; Chvátalová, J; Kunke, D; Filip, S; Mokrý, J

    2016-01-01

    Ensuring mycoplasma-free cell culture is of prime importance as they severely affect cellular characteristics leading to experimental artefacts and spurious results. Various methods persist for mycoplasma detection; out of the whole array of methods polymerase chain reaction (PCR) is the most favoured one because it is highly sensitive, specific and quick. The PCR-based detection procedure involves three steps: cell culture supernatant collection, DNA isolation, and PCR. We have modified this procedure so that cell culture supernatant can directly be used for PCR without the need for DNA extraction. This modification makes the procedure quicker and more sensitive because loss of mycoplasma DNA is prevented and this loss becomes more significant when the level of mycoplasma contamination is very low.

  11. Bifunctional Brønsted Base Catalyzes Direct Asymmetric Aldol Reaction of α-Keto Amides.

    PubMed

    Echave, Haizea; López, Rosa; Palomo, Claudio

    2016-03-01

    The first enantioselective direct cross-aldol reaction of α-keto amides with aldehydes, mediated by a bifunctional ureidopeptide-based Brønsted base catalyst, is described. The appropriate combination of a tertiary amine base and an aminal, and urea hydrogen-bond donor groups in the catalyst structure promoted the exclusive generation of the α-keto amide enolate which reacted with either non-enolizable or enolizable aldehydes to produce highly enantioenriched polyoxygenated aldol adducts without side-products resulting from dehydration, α-keto amide self-condensation, aldehyde enolization, and isotetronic acid formation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Action Video Games Improve Direction Discrimination of Parafoveal Translational Global Motion but Not Reaction Times.

    PubMed

    Pavan, Andrea; Boyce, Matthew; Ghin, Filippo

    2016-10-01

    Playing action video games enhances visual motion perception. However, there is psychophysical evidence that action video games do not improve motion sensitivity for translational global moving patterns presented in fovea. This study investigates global motion perception in action video game players and compares their performance to that of non-action video game players and non-video game players. Stimuli were random dot kinematograms presented in the parafovea. Observers discriminated the motion direction of a target random dot kinematogram presented in one of the four visual quadrants. Action video game players showed lower motion coherence thresholds than the other groups. However, when the task was performed at threshold, we did not find differences between groups in terms of distributions of reaction times. These results suggest that action video games improve visual motion sensitivity in the near periphery of the visual field, rather than speed response.

  13. Efficient and directed peptide bond formation in the gas phase via ion/ion reactions.

    PubMed

    McGee, William M; McLuckey, Scott A

    2014-01-28

    Amide linkages are among the most important chemical bonds in living systems, constituting the connections between amino acids in peptides and proteins. We demonstrate the controlled formation of amide bonds between amino acids or peptides in the gas phase using ion/ion reactions in a mass spectrometer. Individual amino acids or peptides can be prepared as reagents by (i) incorporating gas phase-labile protecting groups to silence otherwise reactive functional groups, such as the N terminus; (ii) converting the carboxyl groups to the active ester of N-hydroxysuccinimide; and (iii) incorporating a charge site. Protonation renders basic sites (nucleophiles) unreactive toward the N-hydroxysuccinimide ester reagents, resulting in sites with the greatest gas phase basicities being, in large part, unreactive. The N-terminal amines of most naturally occurring amino acids have lower gas phase basicities than the side chains of the basic amino acids (i.e., those of histidine, lysine, or arginine). Therefore, reagents may be directed to the N terminus of an existing "anchor" peptide to form an amide bond by protonating the anchor peptide's basic residues, while leaving the N-terminal amine unprotonated and therefore reactive. Reaction efficiencies of greater than 30% have been observed. We propose this method as a step toward the controlled synthesis of peptides in the gas phase.

  14. Direct Determination of the Simplest Criegee Intermediate (CH2OO) Self Reaction Rate.

    PubMed

    Buras, Zachary J; Elsamra, Rehab M I; Green, William H

    2014-07-03

    The rate of self-reaction of the simplest Criegee intermediate, CH2OO, is of importance in many current laboratory experiments where CH2OO concentrations are high, such as flash photolysis and alkene ozonolysis. Using laser flash photolysis while simultaneously probing both CH2OO and I atom by direct absorption, we can accurately determine absolute CH2OO concentrations as well as the UV absorption cross section of CH2OO at our probe wavelength (λ = 375 nm), which is in agreement with a recently published value. Knowing absolute concentrations we can accurately measure kself = 6.0 ± 2.1 × 10(-11)cm(3) molecule(-1) s(-1) at 297 K. We are also able to put an upper bound on the rate coefficient for CH2OO + I of 1.0 × 10(-11) cm(3) molecule(-1) s(-1). Both of these rate coefficients are at least a factor of 5 smaller than other recent measurements of the same reactions.

  15. Direct Numerical Simulation of biomass pyrolysis and combustion with gas phase reactions

    NASA Astrophysics Data System (ADS)

    Awasthi, A.; Kuerten, J. G. M.; Geurts, B. J.

    2016-09-01

    We present Direct Numerical Simulation of biomass pyrolysis and combustion in a turbulent channel flow. The model includes simplified models for biomass pyrolysis and char combustion along with a model for particle tracking. The gas phase is modelled as a mixture of reacting gas species. The gas-particle interactions for mass, momentum, and energy exchange are included by two-way coupling terms. The effect of two-way coupling on the conversion time of biomass particles is found noticeable for particle volume fractions > 10-5. We also observe that at constant volume fraction the effect of two-way coupling increases as the particle size is reduced, due to the higher total heat exchange area in case of smaller particles. The inclusion of gas phase homogeneous reactions in the DNS model decreases the biomass pyrolysis time due to higher gas temperatures. In contrast, including gas phase reactions increases the combustion time of biomass due to the lower concentration of oxygen at the particle surface.

  16. Direct and sensitive detection of a pathogenic protozoan, Toxoplasma gondii, by polymerase chain reaction.

    PubMed Central

    Burg, J L; Grover, C M; Pouletty, P; Boothroyd, J C

    1989-01-01

    We applied the polymerase chain reaction to detection of the pathogenic protozoan Toxoplasma gondii based on our identification of a 35-fold-repetitive gene (the B1 gene) as a target. Using this procedure, we were able to amplify and detect the DNA of a single organism directly from a crude cell lysate. This level of sensitivity also allowed us to detect the B1 gene from purified DNA samples containing as few as 10 parasites in the presence of 100,000 human leukocytes. This is representative of the maximal cellular infiltration (10(5)/ml) in 1 ml of cerebrospinal fluid obtained from patients with toxoplasmic encephalitis. The B1 gene is present and conserved in all six T. gondii strains tested to date, including two isolates from patients with acquired immunodeficiency syndrome. No signal was detected by using this assay and DNAs from a variety of other organisms, including several which might be found in the central nervous system of an immunocompromised host. This combination of sensitivity and specificity should make detection of the B1 gene based on polymerase chain reaction amplification a very useful method for diagnosis of toxoplasmosis both in immunocompromised hosts and in congenitally infected fetuses. Images PMID:2768467

  17. Anode reaction mechanism and crossover in direct dimethyl ether fuel cell

    NASA Astrophysics Data System (ADS)

    Mizutani, Itsuko; Liu, Yan; Mitsushima, Shigenori; Ota, Ken-ichiro; Kamiya, Nobuyuki

    The anode reaction mechanism and the crossover of a direct dimethyl ether fuel cell (DDMEFC) have been investigated. This was done by considering the anode products of the half-cell and DDMEFC experiments. It was found that the CO 2 current efficiency of the DDMEFC was almost 1 at 30-80 °C and that this value was higher than that of a DMFC. The main by-products of the DDMEFC were methyl formate and methanol whose amounts are negligibly small compared to CO 2. With respect to crossover, the influence of DME on the oxygen reduction reaction (ORR) was examined with a half-cell, and the amount of crossover of DME was measured while operating an actually constructed DDMEFC. From these experiments, it was found that DME does not influence the ORR as much as methanol under similar conditions. Furthermore, the amount of crossover of DME decreased with an increase in temperature and current density and it was one-half that of methanol on open circuit and at 80 °C. The CO 2 current efficiency of the DDMEFC is higher than that of a DMFC, and the influence of crossover in the DDMEFC is less than that in the DMFC. Since the temperature dependence of the reactivity of DME is larger than that of methanol, the higher output is expected for the DDMEFC at the elevated temperature. Therefore, the DDMEFC has a promising potential as a portable power source in the future.

  18. Monitoring transcranial direct current stimulation induced changes in cortical excitability during the serial reaction time task.

    PubMed

    Ambrus, Géza Gergely; Chaieb, Leila; Stilling, Roman; Rothkegel, Holger; Antal, Andrea; Paulus, Walter

    2016-03-11

    The measurement of the motor evoked potential (MEP) amplitudes using single pulse transcranial magnetic stimulation (TMS) is a common method to observe changes in motor cortical excitability. The level of cortical excitability has been shown to change during motor learning. Conversely, motor learning can be improved by using anodal transcranial direct current stimulation (tDCS). In the present study, we aimed to monitor cortical excitability changes during an implicit motor learning paradigm, a version of the serial reaction time task (SRTT). Responses from the first dorsal interosseous (FDI) and forearm flexor (FLEX) muscles were recorded before, during and after the performance of the SRTT. Online measurements were combined with anodal, cathodal or sham tDCS for the duration of the SRTT. Negative correlations between the amplitude of online FDI MEPs and SRTT reaction times (RTs) were observed across the learning blocks in the cathodal condition (higher average MEP amplitudes associated with lower RTs) but no significant differences in the anodal and sham conditions. tDCS did not have an impact on SRTT performance, as would be predicted based on previous studies. The offline before-after SRTT MEP amplitudes showed an increase after anodal and a tendency to decrease after cathodal stimulation, but these changes were not significant. The combination of different interventions during tDCS might result in reduced efficacy of the stimulation that in future studies need further attention.

  19. Models of current sintering

    NASA Astrophysics Data System (ADS)

    Angst, Sebastian; Engelke, Lukas; Winterer, Markus; Wolf, Dietrich E.

    2017-06-01

    Densification of (semi-)conducting particle agglomerates with the help of an electrical current is much faster and more energy efficient than traditional thermal sintering or powder compression. Therefore, this method becomes more and more common among experimentalists, engineers, and in industry. The mechanisms at work at the particle scale are highly complex because of the mutual feedback between current and pore structure. This paper extends previous modelling approaches in order to study mixtures of particles of two different materials. In addition to the delivery of Joule heat throughout the sample, especially in current bottlenecks, thermoelectric effects must be taken into account. They lead to segregation or spatial correlations in the particle arrangement. Various model extensions are possible and will be discussed.

  20. pH-dependent electron transfer reaction and direct bioelectrocatalysis of the quinohemoprotein pyranose dehydrogenase

    SciTech Connect

    Takeda, Kouta; Matsumura, Hirotoshi; Ishida, Takuya; Yoshida, Makoto; Igarashi, Kiyohiko; Samejima, Masahiro; Ohno, Hiroyuki; Nakamura, Nobuhumi

    2016-08-26

    A pyranose dehydrogenase from Coprinopsis cinerea (CcPDH) is an extracellular quinohemoeprotein, which consists a b-type cytochrome domain, a pyrroloquinoline-quinone (PQQ) domain, and a family 1-type carbohydrate-binding module. The electron transfer reaction of CcPDH was studied using some electron acceptors and a carbon electrode at various pH levels. Phenazine methosulfate (PMS) reacted directly at the PQQ domain, whereas cytochrome c (cyt c) reacted via the cytochrome domain of intact CcPDH. Thus, electrons are transferred from reduced PQQ in the catalytic domain of CcPDH to heme b in the N-terminal cytochrome domain, which acts as a built-in mediator and transfers electron to a heterogenous electron transfer protein. The optimal pH values of the PMS reduction (pH 6.5) and the cyt c reduction (pH 8.5) differ. The catalytic currents for the oxidation of L-fucose were observed within a range of pH 4.5 to 11. Bioelectrocatalysis of CcPDH based on direct electron transfer demonstrated that the pH profile of the biocatalytic current was similar to the reduction activity of cyt c characters. - Highlights: • pH dependencies of activity were different for the reduction of cyt c and DCPIP. • DET-based bioelectrocatalysis of CcPDH was observed. • The similar pH-dependent profile was found with cyt c and electrode. • The present results suggested that IET reaction of CcPDH shows pH dependence.

  1. Direct kinetic measurements of Criegee intermediate (CH₂OO) formed by reaction of CH₂I with O₂.

    PubMed

    Welz, Oliver; Savee, John D; Osborn, David L; Vasu, Subith S; Percival, Carl J; Shallcross, Dudley E; Taatjes, Craig A

    2012-01-13

    Ozonolysis is a major tropospheric removal mechanism for unsaturated hydrocarbons and proceeds via "Criegee intermediates"--carbonyl oxides--that play a key role in tropospheric oxidation models. However, until recently no gas-phase Criegee intermediate had been observed, and indirect determinations of their reaction kinetics gave derived rate coefficients spanning orders of magnitude. Here, we report direct photoionization mass spectrometric detection of formaldehyde oxide (CH(2)OO) as a product of the reaction of CH(2)I with O(2). This reaction enabled direct laboratory determinations of CH(2)OO kinetics. Upper limits were extracted for reaction rate coefficients with NO and H(2)O. The CH(2)OO reactions with SO(2) and NO(2) proved unexpectedly rapid and imply a substantially greater role of carbonyl oxides in models of tropospheric sulfate and nitrate chemistry than previously assumed.

  2. [Comparison of direct microscopy, culture and polymerase chain reaction methods for the diagnosis of cutaneous leishmaniasis].

    PubMed

    Ertabaklar, Hatice; Özlem Çalışkan, Serçin; Boduç, Erengül; Ertuğ, Sema

    2015-01-01

    Cutaneous leishmaniasis (CL) is an endemic disease especially in Southeastern Anatolia of Turkey and recently shows a trend for spread to other regions of the country including the Aegean region. The diagnosis of CL is based on combined evaluation of epidemiological data with the clinical symptoms and laboratory findings. Direct microscopic examination and culture methods are mainly used in the routine diagnosis of CL, while molecular methods are mainly used for research. The aim of this study was to detect the presence of Leishmania spp. in samples obtained from CL-suspected patients by using direct microscopy, culture and polymerase chain reaction (PCR) methods and to compare the results. A total of 55 patients who were admitted to Parasitology Laboratory of Adnan Menderes University Hospital, Aydin (located at Aegean region in Turkey), between 2012-2014 were included in the study. Smear preparations from the skin lesions of cases were fixed and stained with Giemsa, and the presence of amastigote forms were evaluated by direct microscopy. NNN medium was used for the cultivation of samples. Total genomic DNA of Leishmania from the samples were extracted with a commercial kit (NucleoSpin Tissue(®) Kit, Macherey-Nagel, Germany) and PCR was performed by using 13A and 13B primers to amplify the 116 base pair fragment of Leishmania spp. specific kinetoplast DNA. Amastigotes were observed in 29 (53%) of the 55 samples by direct microscopy, promastigotes were detected among 34 (62%) samples in culture, and parasite-specific amplicons were revealed in 30 (55%) samples by PCR. All assays were positive in 24 patients while in 18 patients all of the tests yielded negative results. Thirty-seven (67%) out of 55 cases were diagnosed as CL when reactivity in at least one of these three methods were considered as positive. Accordingly the positivity rates of the methods were 78.4% (29/37) for direct microscopy, 92% (34/37) for culture and 81.1% (30/37) for PCR in CL

  3. 59Co(p, α) reaction at 100 MeV incident energy - statistical multistep direct reaction into the continuum of outgoing energies

    NASA Astrophysics Data System (ADS)

    Dimitrova, S. S.; Cowley, A. A.; Zemlyanaya, E. V.; Lukyanov, K. V.

    2016-01-01

    The pre-equilibrium proton induced emission of light complex nuclei with energies in the continuum has been studied comprehensively for many years. Double-differential cross sections and especially analyzing power distributions are typical of an intranuclear nucleon-nucleon multistep statistical reaction mechanism. The final stage of the reaction may be a result of a direct pickup or knockout of the ejectile. The discussion on this subject continues to be a hot topic for both theoretical and experimental investigations. In this paper the results from the latest studies of the inclusive (p, α) reactions on 59Co to the continuum will be reported. The formalism based on the statistical multistep direct emission formulation of Feshbach, Kerman and Koonin is found to give a reasonably good reproduction of cross section and analyzing power distributions at various emission energies. Special attention will be paid to the details of the calculations.

  4. Sintering techniques for microstructure control in ceramics

    NASA Astrophysics Data System (ADS)

    Rosenberger, Andrew T.

    Sintering techniques can be manipulated to enhance densification in difficult to sinter materials and to produce property enhancing microstructures. However, the interplay between materials, sintering techniques, and end properties is not fully understood in many material systems, and some fundamental aspects of sintering such as the nature of the effects of electric fields remains unknown. The processing property relationships were examined in two classes of materials; zirconium diboride ultra high temperature ceramic composites, and all solid lithium-ion battery phosphate materials. Investigation of zirconium diboride ceramics focused on the effects of zirconium carbide as a secondary or tertiary phase in ZrB2 and ZrB2 -- SiC. Addition of zirconium carbide was observed to increase flexural strength of composites up to 590MPa at 50wt% ZrC, significantly higher than the flexural strength of 380MPa observed in similarly prepared ZrB2 -- SiC. This difference was attributed to the absence of CTE mismatch induced residual stresses in the ZrB2 -- ZrC composites. A high temperature reaction between ZrB2 and TiC producing Zr1-xTixB2 -- ZrC composites was discovered and found to enhance densification while reducing the average grain size to as small as 1.4mum, lower than the starting powder size of 1.8mum. While a high flexural strength of 670MPa was observed, a strength dependence on the ZrC grain size indicative of CTE mismatch residual stresses was also seen. Finally, the oxidation and ablation resistance of ZrB2 -- ZrC -- SiC composites as a function of ZrC fraction and ZrC:SiC ratio was investigated. Above 5vol% ZrC, the oxidation and ablation resistance of the composites was significantly reduced due to ZrC oxidation, regardless of SiC content. While ZrC can significantly enhance the mechanical properties of the composite, the volume fraction must be kept low to avoid an undesirable reduction in the oxidation resistance. The influence of applied electrical fields

  5. Magnetic field effects on reactive sintering of MnBi

    NASA Astrophysics Data System (ADS)

    Abematsu, Ken-ichi; Mitsui, Yoshifuru; Taira, Atsushi; Miyazaki, Daiki; Takaki, Akio; Umetsu, Rie Y.; Takahashi, Kohki; Koyama, Keiichi

    2016-08-01

    Annealing temperature of reactive sintering of MnBi was optimized. The highest fraction of MnBi phase was obtained to be 93wt.% at annealing temperature of 280°C. Magnetic field effects on solid- and liquid-state sintering of MnBi were described. The reacted fraction of MnBi was enhanced by the application of magnetic field of 15 T for solid- state sintering. In contract, reacted fraction was not influenced by magnetic field for liquid-state sintering. Both of in- field solid- and liquid-state sintered samples realized the highly crystal orientation of MnBi phase along the applied magnetic field direction. The Lotgering factor of the MnBi phase was obtained to be 1.0 for both in-field sintered samples, which was an "almost complete" uniaxial orientation. Due to the crystal orientation, anisotropic magnetic properties exhibited. The anisotropy field of the bulk sample was evaluated to be 4 T at room temperature, which also suggested the uniaxial orientation of the sample.

  6. Direct coupling between stress, strain and adsorption reactions - A study on coal-CO2 systems

    NASA Astrophysics Data System (ADS)

    Hol, S.; Peach, C. J.; Spiers, C. J.

    2012-12-01

    Though it is well-known that adsorption reactions frequently assist deformation of porous rocks, very little understanding exists on the direct coupling with stress state and strain. One of the materials in which adsorption plays a large role is coal, as is observed in the particular case of Enhanced Coalbed Methane Production (ECBM), which involves the geological storage of CO2 and the recovery of CH4. In this case, adsorption and the associated swelling cause significant injectivity problems, which is experienced in almost all pilot field projects to date. This suggests that indeed a strong fundamental coupling exists between CO2 sorption, changes in the mechanical state of the coal matrix and changes in the transport properties of the system, and illustrates the need to understand coupled stress-strain-sorption behaviour. In this contribution, we describe several important observations made on coal-CO2 systems that can learn us about many other natural, stressed adsorbate-adsorbent systems. In our experiments, first of all, the adsorption of CO2 in the coal matrix gave rise to swelling. Although this is well-known, we found that the total volumetric strain occurring under unconfined conditions can be realistically modelled (up to at least 100 MPa) as the sum of an adsorption-related expansion term and an elastic compression term. Second, effective in situ stresses will directly reduce the sorption capacity, and associated swelling of the coal matrix significantly. Our general thermodynamic model for the effect of a 3D stress state on adsorbed CO2 concentration supports this observation, and also shows that "self-stressing", as a result of CO2 adsorption occurring under conditions of restricted or zero strain (i.e. fully constrained conditions), will more than double the expected in situ stresses. A constitutive equation was developed to describe the full coupling between stress state, total strain (i.e. combined strain of adsorption processes and poroelasticity

  7. One step sintering of homogenized bauxite raw material and kinetic study

    NASA Astrophysics Data System (ADS)

    Gao, Chang-he; Jiang, Peng; Li, Yong; Sun, Jia-lin; Zhang, Jun-jie; Yang, Huan-ying

    2016-10-01

    A one-step sintering process of bauxite raw material from direct mining was completed, and the kinetics of this process was analyzed thoroughly. The results show that the sintering kinetics of bauxite raw material exhibits the liquid-phase sintering behavior. A small portion of impurities existed in the raw material act as a liquid phase. After X-ray diffraction analyses, scanning electron microscopy observations, and kinetics calculations, sintering temperature and heating duration were determined as the two major factors contributing to the sintering process and densification of bauxite ore. An elevated heating temperature and longer duration favor the densification process. The major obstacle for the densification of bauxite material is attributed to the formation of the enclosed blowhole during liquid-phase sintering.

  8. Electrical sintering of nanoparticle structures.

    PubMed

    Allen, Mark L; Aronniemi, Mikko; Mattila, Tomi; Alastalo, Ari; Ojanperä, Kimmo; Suhonen, Mika; Seppä, Heikki

    2008-04-30

    A method for sintering nanoparticles by applying voltage is presented. This electrical sintering method is demonstrated using silver nanoparticle structures ink-jet-printed onto temperature-sensitive photopaper. The conductivity of the printed nanoparticle layer increases by more than five orders of magnitude during the sintering process, with the final conductivity reaching 3.7 × 10(7) S m(-1) at best. Due to a strong positive feedback induced by the voltage boundary condition, the process is very rapid-the major transition occurs within 2 µs. The best obtained conductivity is two orders of magnitude better than for the equivalent structures oven-sintered at the maximum tolerable temperature of the substrate. Additional key advantages of the method include the feasibility for patterning, systematic control of the final conductivity and in situ process monitoring. The method offers a generic tool for electrical functionalization of nanoparticle structures.

  9. Ceramic powder for sintering materials

    NASA Technical Reports Server (NTRS)

    Akiya, H.; Saito, A.

    1984-01-01

    Surface activity of ceramic powders such as MgO and Al2O3, for use in sintering with sp. emphasis on their particle size, shape, particle size distribution, packing, and coexisting additives and impurities are reviewed.

  10. Electrical Sintering of Silver Nanoparticle Ink Studied by In-Situ TEM Probing

    PubMed Central

    Hummelgård, Magnus; Zhang, Renyun; Nilsson, Hans-Erik; Olin, Håkan

    2011-01-01

    Metallic nanoparticle inks are used for printed electronics, but to reach acceptable conductivity the structures need to be sintered, usually using a furnace. Recently, sintering by direct resistive heating has been demonstrated. For a microscopic understanding of this Joule heating sintering method, we studied the entire process in real time inside a transmission electron microscope equipped with a movable electrical probe. We found an onset of Joule heating induced sintering and coalescence of nanoparticles at power levels of 0.1–10 mW/m3. In addition, a carbonization of the organic shells that stabilize the nanoparticles were found, with a conductivity of 4 105 Sm−1. PMID:21390314

  11. Estimation of Sintering Kinetics of Oxidized Magnetite Pellet Using Optical Dilatometer

    NASA Astrophysics Data System (ADS)

    Sandeep Kumar, T. K.; Viswanathan, Neelakantan Nurni; Ahmed, Hesham M.; Andersson, Charlotte; Björkman, Bo

    2015-04-01

    The quality of magnetite pellet is primarily determined by the physico-chemical changes the pellet undergoes as it makes excursion through the gaseous and thermal environment in the induration furnace. Among these physico-chemical processes, the oxidation of magnetite phase and the sintering of oxidized magnetite (hematite) and magnetite (non-oxidized) phases are vital. Rates of these processes not only depend on the thermal and gaseous environment the pellet gets exposed in the induration reactor but also interdependent on each other. Therefore, a systematic study should involve understanding these processes in isolation to the extent possible and quantify them seeking the physics. With this motivation, the present paper focusses on investigating the sintering kinetics of oxidized magnetite pellet. For the current investigation, sintering experiments were carried out on pellets containing more than 95 pct magnetite concentrate from LKAB's mine, dried and oxidized to completion at sufficiently low temperature to avoid sintering. The sintering behavior of this oxidized pellet is quantified through shrinkage captured by Optical Dilatometer. The extent of sintering characterized by sintering ratio found to follow a power law with time i.e., Kt n . The rate constant K for sintering was determined for different temperatures from isothermal experiments. The rate constant, K, varies with temperature as and the activation energy ( Q) and reaction rate constant ( K') are estimated. Further, the sintering kinetic equation was also extended to a non-isothermal environment and validated using laboratory experiments.

  12. The effects of sintering temperature on dielectric constant of Barium Titanate (BaTiO3)

    NASA Astrophysics Data System (ADS)

    Sandi, DianisaKhoirum; Supriyanto, Agus; Anif; Jamaluddin; Iriani, Yofentina

    2016-02-01

    Barium Titanate (BT) has been synthesized using solid-state reaction method. Raw materials are Barium Carbonate (BaCO3) and Titanium Dioxide (TiO2). These materials are mixed for 6 h and sintered at a temperature of 1000oC, 1100oC, and 1200oC for 2 h. The sintering temperature was varied to investigate its effects on microstructure and dielectric constant of BT. The XRD patterns showed that BT becomes homogenous, with the large lattice parameter as the increase of sintering temperature. The crystal structure of BT is tetragonal. The crystalline size and crystallinity of BT at a sintering temperature of 1000oC are 37 nm and 97%. Those values for BT at a sintering temperature of 1100oC are 38 nm and 96%. At a sintering temperature of 1200oC, the values are 41 nm and 97%. The dielectric constant of BT at a sintering temperature of 1000oC, 1100oC, and 1200oC are 148, 163, and 185, respectively. It can be concluded that sintering temperature affects microstructure and dielectric constant of BT. High sintering temperature produces a high dielectric constant of BT. It indicates that crystalline size increases.

  13. Method of sintering ceramic materials

    DOEpatents

    Holcombe, Cressie E.; Dykes, Norman L.

    1992-01-01

    A method for sintering ceramic materials is described. A ceramic article is coated with layers of protective coatings such as boron nitride, graphite foil, and niobium. The coated ceramic article is embedded in a container containing refractory metal oxide granules and placed within a microwave oven. The ceramic article is heated by microwave energy to a temperature sufficient to sinter the ceramic article to form a densified ceramic article having a density equal to or greater than 90% of theoretical density.

  14. Method of sintering ceramic materials

    DOEpatents

    Holcombe, C.E.; Dykes, N.L.

    1992-11-17

    A method for sintering ceramic materials is described. A ceramic article is coated with layers of protective coatings such as boron nitride, graphite foil, and niobium. The coated ceramic article is embedded in a container containing refractory metal oxide granules and placed within a microwave oven. The ceramic article is heated by microwave energy to a temperature sufficient to sinter the ceramic article to form a densified ceramic article having a density equal to or greater than 90% of theoretical density. 2 figs.

  15. The sintering of nitrogen ceramics

    SciTech Connect

    Hampshire, S.

    1986-01-01

    The mechanism of densification with oxide additives and the role of the ..cap alpha..-BETA phase transformation is investigated in a detailed kinetic study. Selected compositions in the Si-Al-O-N system are detailed, with and without additives. Although the work is mainly concerned with the identification of the mechanisms of sintering, some property measurements on a sintered BETA-sialon are reported and the feasibility of preparing pure ..cap alpha..-sialon phases is explored.

  16. PLANETESIMAL FORMATION INDUCED BY SINTERING

    SciTech Connect

    Sirono, Sin-iti

    2011-06-01

    Sintering of H{sub 2}O ice proceeds in an icy dust aggregate as the temperature increases due to the infall to the central star. By numerical simulations, I show that fragmentation of the aggregate by sintering occurs at a particular region of a protoplanetary nebula. The fragments accumulate at the region because their infalling velocity is low. The dust surface density exceeds the critical surface density required for gravitational instability to form planetesimals.

  17. Optimization of the sintering atmosphere for high-density hydroxyapatite-carbon nanotube composites.

    PubMed

    White, Ashley A; Kinloch, Ian A; Windle, Alan H; Best, Serena M

    2010-10-06

    Hydroxyapatite-carbon nanotube (HA-CNT) composites have the potential for improved mechanical properties over HA for use in bone graft applications. Finding an appropriate sintering atmosphere for this composite presents a dilemma, as HA requires water in the sintering atmosphere to remain phase pure and well hydroxylated, yet CNTs oxidize at the high temperatures required for sintering. The purpose of this study was to optimize the atmosphere for sintering these composites. While the reaction between carbon and water to form carbon monoxide and hydrogen at high temperatures (known as the 'water-gas reaction') would seem to present a problem for sintering these composites, Le Chatelier's principle suggests this reaction can be suppressed by increasing the concentration of carbon monoxide and hydrogen relative to the concentration of carbon and water, so as to retain the CNTs and keep the HA's structure intact. Eight sintering atmospheres were investigated, including standard atmospheres (such as air and wet Ar), as well as atmospheres based on the water-gas reaction. It was found that sintering in an atmosphere of carbon monoxide and hydrogen, with a small amount of water added, resulted in an optimal combination of phase purity, hydroxylation, CNT retention and density.

  18. Choice reaction times for human head rotations are shortened by startling acoustic stimuli, irrespective of stimulus direction.

    PubMed

    Oude Nijhuis, Lars B; Janssen, Loes; Bloem, Bastiaan R; van Dijk, J Gert; Gielen, Stan C; Borm, George F; Overeem, Sebastiaan

    2007-10-01

    Auditory startle reflexes can accelerate simple voluntary reaction times (StartReact effect). To investigate the role of startle reflexes on more complex motor behaviour we formulated two questions: (1) can auditory startle reflexes shorten choice reaction times?; (2) is the StartReact effect differentially modulated when startling auditory stimuli are delivered ipsilaterally or contralaterally to an imperative 'go' signal? We instructed 16 healthy subjects to rotate their head as rapidly as possible to the left or to right in response to a guiding visual imperative stimulus (IS), in both a simple and choice reaction protocol. Startling acoustic stimuli (113 dB) were delivered simultaneously with the IS (from either the same or opposite side) to induce the StartReact effect. We recorded kinematics of head rotations and electromyographic responses. The StartReact effect was present during choice reaction tasks (56 ms onset reduction; P < 0.001). The presentation side of the startling stimulus (left/right) did not influence the effect in choice reaction tasks. We observed a directional effect in simple reaction tasks, but this probably occurred due to a flooring effect of reaction times. Onsets of EMG responses in neck muscles were not influenced by the direction of the acoustic startling stimulus. Startling acoustic stimuli decrease reaction times not only in simple but also in choice reaction time tasks, suggesting that startle reflexes can accelerate adequate human motor responses. The absence of a clear directional sensitivity of reaction times to startling acoustic stimuli suggests that the acceleration is not highly specific, but seems to provide a global preparatory effect upon which further tailored action can be undertaken more quickly.

  19. Direct observation of spin-like reaction fronts in planar energetic multilayer foils.

    SciTech Connect

    Adams, David Price; Hodges, V. Carter; Jones, Eric D., Jr.; McDonald, Joel Patrick

    2008-10-01

    Propagating reactions in initially planar cobalt/aluminum exothermic multilayer foils have been investigated using high-speed digital photography. Real-time observations of reactions indicate that unsteady (spinlike) reaction propagation leads to the formation of highly periodic surface morphologies with length scales ranging from 1 {micro}m to 1 mm. The characteristics of propagating spinlike reactions and corresponding reacted foil morphologies depend on the bilayer thickness of multilayer foils.

  20. Characteristic variation of spark plasma-sintered Ta compacts

    NASA Astrophysics Data System (ADS)

    Cho, Gue-Serb; Lim, Jung-Kyu; Choe, Kyeong-Hwan; Shin, Seung-Yong

    2010-05-01

    In the present study, we applied the SPS process to obtain a tantalum (Ta) compact for a sputtering target. Sintered Ta compacts were characterized with respect to microstructure, relative density, Vickers hardness and phase composition of the inside and the surface. By radio frequency (RF) thermal plasma treatment, a spherical ultra-fine Ta powder was obtained; however, the oxygen content increased due to severe passivation during powder handling. Higher sintering temperature and the RF plasma treatment increased the densification of the sintered compact and also the Vickers hardness. From XRD analysis, only Ta was identified in the cross section of compacts, and TaC formed by the reaction between Ta and the graphite mould was found in the surface of the compacts. The evacuation of the chamber and the reduction by the graphite mould promote the purification of the compact.

  1. Zrb2 nanoparticle cluster reinforced Al matrix composites fabricated by direct melt reaction

    NASA Astrophysics Data System (ADS)

    Zhang, Zhenya; Yang, Rui; Liu, Menglu; Yue, Yamei; Tang, Zhenming; Meng, Mingai; Jiao, Lei

    2017-01-01

    In this work, ZrB2 nanoparticle cluster reinforced 6061Al composites were synthesized by direct melt reaction between halide salts (KBF4 and K2ZrF6) and Al. The experimental results revealed that the formation of Type III cluster (>60 µm, grain interior) depended on ZrB2 addition levels (>2 vol. %), whilst Type I (˜5 µm, grain interior) and II (5˜60 µm, grain/ interdendritic boundaries) were always present. The optimum tensile strength and elongation obtained in 2vol. % ZrB2/6061Al composite were substantially improved to approximately 1.52 and 2.75 times those of the 6061Al alloy. The enhanced strength was attributed to a combination effect of grain refinement (Type II cluster) and Orowan/CTE strengthening (Type I cluster). On the other hand, the impressive ductility increase was also ascribed to the presence of toughened clusters (Type I and II) that introduced the plastic slip bands and equiaxed dimples.

  2. Direct Excitation of the Reaction Coordinate: Overtone-Induced Predissociation of the Hydroxymethyl Radical

    NASA Astrophysics Data System (ADS)

    Reisler, Hanna; Ryazanov, Mikhail; Rodrigo, Chirantha P.

    2011-06-01

    The overtone-induced vibrational predissociation of the hydroxymethyl radical is achieved following excitation of the radical to the third O-H stretch overtone. The excited O-H stretch is also the bond that breaks; i.e. overtone excitation is in the reaction coordinate. The production of H atoms takes place via tunneling through the barrier to the H + formaldehyde channel. H-atom photofragment yield spectra in the region of the third overtone reveal two mixed bands with contributions from the third OH overtone and a combination band comprised of two quanta of OH stretch and one quantum of CH asymmetric stretch. Using velocity map imaging, sliced images of H-atom products are obtained with kinetic energy resolution sufficient to reveal the vibrational structure in the formaldehyde co-fragment. As expected, most of the formaldehyde molecules are born without vibrational excitation but some exhibit excitation in other modes, such as wagging and CO stretch. The rotational contours of the vibrational bands are well described by temperatures in the range 100-150 K. Slice imaging allows scanning the pump laser while monitoring H fragments in selected kinetic energy ranges, and in this way it is demonstrated that all the observed vibrational levels of formaldehyde have their parentage in the hydroxymethyl radical. The barrier to isomerization to methoxy is comparable to the barrier to direct dissociation and the role of isomerization is investigated by using partially deuterated radicals.

  3. MORATE: a program for direct dynamics calculations of chemical reaction rates by semiempirical molecular orbital theory

    NASA Astrophysics Data System (ADS)

    Truong, Thanh N.; Lu, Da-hong; Lynch, Gillian C.; Liu, Yi-Ping; Melissas, Vasilios S.; Stewart, James J. P.; Steckler, Rozeanne; Garrett, Bruce C.; Isaacson, Alan D.; Gonzalez-Lafont, Angels; Rai, Sachchida N.; Hancock, Gene C.; Joseph, Tomi; Truhlar, Donald G.

    1993-04-01

    We present a computer program, MORATE (Molecular Orbital RATE calculations), for direct dynamics calculations of unimolecular and bimolecular rate constants of gas-phase chemical reactions involving atoms, diatoms, or polyatomic species. The potential energies, gradients, and higher derivatives of the potential are calculated whenever needed by semiempirical molecular orbital theory without the intermediary of a global or semiglobal fit. The dynamical methods used are conventional or variational transition state theory and multidimensional semiclassical approximations for tunneling and nonclassical reflection. The computer program is conveniently interfaced package consisting of the POLYRATE program, version 4.5.1, for dynamical rate calculations, and the MOPAC program, version 5.03, for semiempirical electronic structure computations. All semiempirical methods available in MOPAC, in particular MINDO/3, MNDO, AM1, and PM3, can be called on to calculate the potential and gradient. Higher derivatives of the potential are obtained by numerical derivatives of the gradient. Variational transition states are found by a one-dimensional search of generalized-transition-state dividing surfaces perpendicular to the minimum-energy path, and tunneling probabilities are evaluated by numerical quadrature.

  4. Catalytic Direct-type 1,4-Addition Reactions of Alkylazaarenes.

    PubMed

    Suzuki, Hirotsugu; Igarashi, Ryo; Yamashita, Yasuhiro; Kobayashi, Shū

    2017-04-10

    1,4-addition reactions of alkylazaarenes catalyzed by strong Brønsted bases have been developed for the first time. The desired reactions with α,β-unsaturated amides proceeded under mild reaction conditions to give the 1,4-adducts in high yields. Both ortho- and para-substituted azaarenes afforded the desired adducts in high yields. Regioselective reactions of di- or trimethylpyridine were found to be possible depending on the acidity of the α-hydrogen atoms. Furthermore, a candidate of allosteric protein kinase modulators was synthesized in two steps. An asymmetric variant of this reaction was also found to be feasible.

  5. Enantioselective Direct Mannich-Type Reactions Catalyzed by Frustrated Lewis Acid/Brønsted Base Complexes.

    PubMed

    Shang, Ming; Cao, Min; Wang, Qifan; Wasa, Masayuki

    2017-09-05

    An enantioselective direct Mannich-type reaction catalyzed by a sterically frustrated Lewis acid/Brønsted base complex is disclosed. Cooperative functioning of the chiral Lewis acid and achiral Brønsted base components gives rise to in situ enolate generation from monocarbonyl compounds. Subsequent reaction with hydrogen-bond-activated aldimines delivers β-aminocarbonyl compounds with high enantiomeric purity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Direct dynamics simulations of the product channels and atomistic mechanisms for the OH(-) + CH3I reaction. Comparison with experiment.

    PubMed

    Xie, Jing; Sun, Rui; Siebert, Matthew R; Otto, Rico; Wester, Roland; Hase, William L

    2013-08-15

    Electronic structure and direct dynamics calculations were used to study the potential energy surface and atomic-level dynamics for the OH(-) + CH3I reactions. The results are compared with crossed molecular beam, ion imaging experiments. The DFT/B97-1/ECP/d level of theory gives reaction energetics in good agreement with experiment and higher level calculations, and it was used for the direct dynamics simulations that were performed for reactant collision energies of 2.0, 1.0, 0.5, and 0.05 eV. Five different pathways are observed in the simulations, forming CH3OH + I(-), CH2I(-) + H2O, CH2 + I(-) + H2O, IOH(-) + CH3, and [CH3--I--OH](-). The SN2 first pathway and the proton-transfer second pathway dominate the reaction dynamics. Though the reaction energetics favor the SN2 pathway, the proton-transfer pathway is more important except for the lowest collision energy. The relative ion yield determined from the simulations is in overall good agreement with experiment. Both the SN2 and proton-transfer pathways occur via direct rebound, direct stripping, and indirect mechanisms. Except for the highest collision energy, 70-90% of the indirect reaction for the SN2 pathway occurs via formation of the hydrogen-bonded OH(-)---HCH2I prereaction complex. For the proton-transfer pathway the indirect reaction is more complex with the roundabout mechanism and formation of the OH(-)---HCH2I and CH2I(-)---HOH complexes contributing to the reaction. The majority of the SN2 reaction is direct at 2.0, 1.0, and 0.5 eV, dominated by stripping. At 0.05 eV the two direct mechanisms and the indirect mechanisms have nearly equal contributions. The majority of the proton-transfer pathway is direct stripping at 2.0, 1.0, and 0.5 eV, but the majority of the reaction is indirect at 0.05 eV. The product relative translational energy distributions are in good agreement with experiment for both the SN2 and proton-transfer pathways. For both, direct reaction preferentially transfers the product

  7. A New Direct Single-Molecule Observation Method for DNA Synthesis Reaction Using Fluorescent Replication Protein A

    PubMed Central

    Takahashi, Shunsuke; Kawasaki, Shohei; Miyata, Hidefumi; Kurita, Hirofumi; Mizuno, Takeshi; Matsuura, Shun-ichi; Mizuno, Akira; Oshige, Masahiko; Katsura, Shinji

    2014-01-01

    Using a single-stranded region tracing system, single-molecule DNA synthesis reactions were directly observed in microflow channels. The direct single-molecule observations of DNA synthesis were labeled with a fusion protein consisting of the ssDNA-binding domain of a 70-kDa subunit of replication protein A and enhanced yellow fluorescent protein (RPA-YFP). Our method was suitable for measurement of DNA synthesis reaction rates with control of the ssλDNA form as stretched ssλDNA (+flow) and random coiled ssλDNA (−flow) via buffer flow. Sequentially captured photographs demonstrated that the synthesized region of an ssλDNA molecule monotonously increased with the reaction time. The DNA synthesis reaction rate of random coiled ssλDNA (−flow) was nearly the same as that measured in a previous ensemble molecule experiment (52 vs. 50 bases/s). This suggested that the random coiled form of DNA (−flow) reflected the DNA form in the bulk experiment in the case of DNA synthesis reactions. In addition, the DNA synthesis reaction rate of stretched ssλDNA (+flow) was approximately 75% higher than that of random coiled ssλDNA (−flow) (91 vs. 52 bases/s). The DNA synthesis reaction rate of the Klenow fragment (3′-5′exo–) was promoted by DNA stretching with buffer flow. PMID:24625741

  8. Bonding Strength of Ceromer with Direct Laser Sintered, Ni-Cr-Based, and ZrO2 Metal Infrastructures After Er:YAG, Nd:YAG, and Ho:YAG Laser Surface Treatments-A Comparative In Vitro Study.

    PubMed

    Gorler, Oguzhan; Ozdemir, Ali Kemal

    2016-08-01

    Laser modalities instead of conventional surface treatment techniques have been suggested to obtain an adequate micromechanical bonding between dental super- and infrastructures. The present study was undertaken to assess the effect of surface treatment with Ho:YAG, Er:YAG, and Nd:YAG laser modalities on the shear bond strength (SBS) of ceromer to different types of metal infrastructures in in vitro settings. The study specimens consisted of 40 direct laser sintered (DLS), 40 Ni-Cr-based, and 40 zirconium oxide (ZrO2) infrastructures. In each infrastructure group, the specimens were divided randomly into five treatment modalities (n = 8): no treatment (controls), sandblasting, Er:YAG, Nd:YAG, and Ho:YAG lasers. The DLS, Ni-Cr-based, and ZrO2 infrastructures were prepared in the final dimensions of 7 mm in diameter and 3 mm in thickness in line with the ISO 11405 standard. Ceromer as superstructure was applied to all the infrastructures after their surface treatments according to the selected treatment modality. SBS test was performed to test the effectiveness of surface treatments. A stereomicroscope was used to determine the changes in the surface morphology of specimens. Among the laser modalities and sandblasting, Ho:YAG laser caused the most important increase in the DLS and Ni-Cr-based infrastructures but sandblasting caused the most important increase in the ZrO2 infrastructure. In all the infrastructures, Nd:YAG laser has the least effectiveness, and Er:YAG laser makes an intermediate success. The stereomicroscopy images presented that the applications of laser surface treatments altered the surface in all the infrastructures. Overall, in current experimental settings, Ho:YAG, Nd:YAG, and Er:YAG lasers, in order of strength, are effective in improving the bonding of ceromer to all the infrastructures. Ho:YAG laser is more effective in the DLS and Ni-Cr-based infrastructures, but sandblasting is more effective in the ZrO2 infrastructure. The studied

  9. Comparison of TiO2 photocatalysis, electrochemically assisted Fenton reaction and direct electrochemistry for simulation of phase I metabolism reactions of drugs.

    PubMed

    Ruokolainen, Miina; Gul, Turan; Permentier, Hjalmar; Sikanen, Tiina; Kostiainen, Risto; Kotiaho, Tapio

    2016-02-15

    The feasibility of titanium dioxide (TiO2) photocatalysis, electrochemically assisted Fenton reaction (EC-Fenton) and direct electrochemical oxidation (EC) for simulation of phase I metabolism of drugs was studied by comparing the reaction products of buspirone, promazine, testosterone and 7-ethoxycoumarin with phase I metabolites of the same compounds produced in vitro by human liver microsomes (HLM). Reaction products were analysed by UHPLC-MS. TiO2 photocatalysis simulated the in vitro phase I metabolism in HLM more comprehensively than did EC-Fenton or EC. Even though TiO2 photocatalysis, EC-Fenton and EC do not allow comprehensive prediction of phase I metabolism, all three methods produce several important metabolites without the need for demanding purification steps to remove the biological matrix. Importantly, TiO2 photocatalysis produces aliphatic and aromatic hydroxylation products where direct EC fails. Furthermore, TiO2 photocatalysis is an extremely rapid, simple and inexpensive way to generate oxidation products in a clean matrix and the reaction can be simply initiated and quenched by switching the UV lamp on/off. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Production of reactive sintered nickel aluminide

    SciTech Connect

    Cooper, R.M.

    1993-01-01

    Effort over the past 3 months was directed at increasing manufacturing capacity (ball milling) and improving product quality. Orders for the powder have increased, mainly for plasma spray powders. NiAl is an excellent coat between a metal and a ceramic, and its use instead of cobalt should extending operating range for carbide tools. The feather phase in the sintered Ni[sub 3]Al was identified to be a Ni-rich phase nucleated on the grain boundaries with 10 wt % Al composition. The ductile to brittle temperature of powder extruded NiAl was found to be between 500 and 600 C, and shows a 50% elongation at 600 C.

  11. Direct polymerase chain reaction for detection of toxigenic Corynebacterium diphtheriae strains from the Republic of Georgia after prolonged storage.

    PubMed

    Kobaidze, K; Popovic, T; Nakao, H; Quick, L

    2000-02-01

    A total of 226 paired nose and throat swab specimens from 113 clinical diphtheria cases from the republic of Georgia were analyzed by direct polymerase chain reaction targeting both A and B subunits of the diphtheria toxin gene, tox. Even after prolonged transport and extensive storage (7-14 months) of the clinical specimens in silica gel packages, direct polymerase chain reaction detected the diphtheria tox gene in 54% of the specimens. Specimens obtained by throat swab were three times more likely than those obtained by nose swab to be positive for Corynebacterium diphtheriae.

  12. Adverse Reactions Due to Directly Observed Treatment Strategy Therapy in Chinese Tuberculosis Patients: A Prospective Study

    PubMed Central

    Lv, Xiaozhen; Tang, Shaowen; Xia, Yinyin; Wang, Xiaomeng; Yuan, Yanli; Hu, Daiyu; Liu, Feiying; Wu, Shanshan; Zhang, Yuan; Yang, Zhirong; Tu, Dehua; Chen, Yixin; Deng, Peiyuan; Ma, Yu; Chen, Ru; Zhan, Siyan

    2013-01-01

    Background More than 1 million tuberculosis (TB) patients are receiving directly observed treatment strategy (DOTS) therapy in China every year. As to the profile of adverse drug reactions (ADRs) due to DOTS therapy, no consensus has been reached. There is no report regarding ADRs due to DOTS therapy with a large Chinese TB population. This study aimed to determine the incidence and prognosis of ADRs due to DOTS therapy, and to evaluate their impact on anti-TB treatment in China. Methods A prospective population-based cohort study was performed during 2007–2008. Sputum smear positive pulmonary TB patients who received DOTS therapy were included and followed up for six to nine months in 52 counties of four regions in China. The suspected ADRs were recorded and reviewed by Chinese State Food and Drug Administration. Results A total of 4304 TB patients were included in this study. 649 patients (15.08%) showed at least one ADR and 766 cases in total were detected. The incidence (count) of ADR based on affected organ was: liver dysfunction 6.34% (273), gastrointestinal disorders 3.74% (161), arthralgia 2.51% (108), allergic reactions 2.35% (101), neurological system disorders 2.04% (88), renal impairment 0.07% (3) and others 0.05% (2). Most cases of ADRs (95%) had a good clinical outcome, while two with hepatotoxicity and one with renal impairment died. Compared with patients without ADRs, patients with ADRs were more likely to have positive smear test results at the end of the intensive phase (adjusted OR, 2.00; 95%CI, 1.44–2.78) and unsuccessful anti-TB outcomes (adjusted OR, 2.58; 95%CI, 1.43–4.68). Conclusions The incidence of ADRs due to DOTS therapy was 15.08%. Those ADRs had a substantial impact on TB control in China. This highlighted the importance of developing strategies to ameliorate ADRs both to improve the quality of patient care and to control TB safely. PMID:23750225

  13. Dual-level direct dynamics studies for the reactions of OH radical with bromine-substituted ethanes.

    PubMed

    Wang, Li; Liu, Jing-yao; Gao, Hong; Wan, Su-qin; Li, Ze-sheng

    2009-03-01

    The dynamic properties of the multichannel hydrogen abstraction reactions of CH(3)CH(2)Br + OH --> products and CH(3)CHBr(2) + OH --> products are studied by dual-level direct dynamics method. For each reaction, three reaction channels, one for alpha-hydrogen abstraction and two for beta-hydrogen abstractions, have been identified. The minimum energy paths (MEPs) of both the reactions are calculated at the Becke's half-and-half (BH&H)-Lee-Yang-Parr (LYP)/6-311G(d, p) level and the energy profiles along the MEPs are further refined with interpolated single-point energies (ISPE) method at the G2M(RCC5)//BH&H-LYP level. There are complexes with energies less than those of the reactants or products located at the entrance or exit channels, which indicates that the reactions may proceed via an indirect mechanism. By canonical variational transition-state theory (CVT) the rate constants are calculated incorporating the small-curvature tunneling (SCT) correction in the temperature range of 220-2000 K. The agreement of the rate constants with available experimental values for two reactions is good in the measured temperature range. The calculated results show that alpha-hydrogen abstraction channel is the major reaction pathway in the lower temperature for two reactions, while the contribution of beta-hydrogen abstraction will increase with the increase in temperature.

  14. Influence of sintering temperature on structure, microstructure and piezoelectric properties of doped BZT-BCT ceramics

    NASA Astrophysics Data System (ADS)

    Dang, Anh Tuan; Vo, Thanh Tung; Truong, Van Chuong; Le, Van Hong

    2017-01-01

    This work reports the influence of sintering temperature on structure, microstructure and piezoelectric properties of 0.48 Ba(Zr0.2Ti0.8)O3-0.52 (Ba0.7Ca0.3)TiO3(BZT-BCT) doped with ZnO nanoparticle ceramics manufactured by a conventional solid state reaction method. By increasing sintering temperature, the piezoelectric behaviors were improved and rose up to the best parameters at a sintering temperature of 1450∘C (d33 = 576 pC/N and kp = 0.55). The corresponding properties of undoped BZT-BCT ceramics were investigated as a comparison. The received results show that the sintering behavior and piezo-parameters of doped BZT-BCT samples are better than the undoped BZT-BCT samples at each sintering temperature.

  15. New Direction in Hydrogeochemical Transport Modeling: Incorporating Multiple Kinetic and Equilibrium Reaction Pathways

    SciTech Connect

    Steefel, C.I.

    2000-02-02

    At least two distinct kinds of hydrogeochemical models have evolved historically for use in analyzing contaminant transport, but each has important limitations. One kind, focusing on organic contaminants, treats biodegradation reactions as parts of relatively simple kinetic reaction networks with no or limited coupling to aqueous and surface complexation and mineral dissolution/precipitation reactions. A second kind, evolving out of the speciation and reaction path codes, is capable of handling a comprehensive suite of multicomponent complexation (aqueous and surface) and mineral precipitation and dissolution reactions, but has not been able to treat reaction networks characterized by partial redox disequilibrium and multiple kinetic pathways. More recently, various investigators have begun to consider biodegradation reactions in the context of comprehensive equilibrium and kinetic reaction networks (e.g. Hunter et al. 1998, Mayer 1999). Here we explore two examples of multiple equilibrium and kinetic reaction pathways using the reactive transport code GIMRT98 (Steefel, in prep.): (1) a computational example involving the generation of acid mine drainage due to oxidation of pyrite, and (2) a computational/field example where the rates of chlorinated VOC degradation are linked to the rates of major redox processes occurring in organic-rich wetland sediments overlying a contaminated aerobic aquifer.

  16. Removable partial denture alloys processed by laser-sintering technique.

    PubMed

    Alageel, Omar; Abdallah, Mohamed-Nur; Alsheghri, Ammar; Song, Jun; Caron, Eric; Tamimi, Faleh

    2017-05-31

    Removable partial dentures (RPDs) are traditionally made using a casting technique. New additive manufacturing processes based on laser sintering has been developed for quick fabrication of RPDs metal frameworks at low cost. The objective of this study was to characterize the mechanical, physical, and biocompatibility properties of RPD cobalt-chromium (Co-Cr) alloys produced by two laser-sintering systems and compare them to those prepared using traditional casting methods. The laser-sintered Co-Cr alloys were processed by the selective laser-sintering method (SLS) and the direct metal laser-sintering (DMLS) method using the Phenix system (L-1) and EOS system (L-2), respectively. L-1 and L-2 techniques were 8 and 3.5 times more precise than the casting (CC) technique (p < 0.05). Co-Cr alloys processed by L-1 and L-2 showed higher (p < 0.05) hardness (14-19%), yield strength (10-13%), and fatigue resistance (71-72%) compared to CC alloys. This was probably due to their smaller grain size and higher microstructural homogeneity. All Co-Cr alloys exhibited low porosity (2.1-3.3%); however, pore distribution was more homogenous in L-1 and L-2 alloys when compared to CC alloys. Both laser-sintered and cast alloys were biocompatible. In conclusion, laser-sintered alloys are more precise and present better mechanical and fatigue properties than cast alloys for RPDs. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2017. © 2017 Wiley Periodicals, Inc.

  17. The Influence of Spark Plasma Sintering Temperature on the Microstructure and Thermoelectric Properties of Al,Ga Dual-Doped ZnO

    NASA Astrophysics Data System (ADS)

    Han, Li; Hung, Le Thanh; van Nong, Ngo; Pryds, Nini; Linderoth, Søren

    2013-07-01

    ZnO dual-doped with Al and Ga was prepared by spark plasma sintering using different sintering temperatures. The microstructural evolution and thermoelectric properties of the samples were investigated in detail. The samples obtained with sintering temperature above 1223 K had higher relative densities and higher electronic conductivity than the sample sintered at 1073 K. These results were supported by the solid-state reaction completion rate, which suggested that sintering temperature above 1223 K would be preferable for complete solid-state reaction of the samples. The sintering mechanism of ZnO particles and microstructure evolution at different sintering temperatures were investigated by simulation of the self-Joule-heating effect of the individual particles.

  18. Magnesium stearine production via direct reaction of palm stearine and magnesium hydroxide

    NASA Astrophysics Data System (ADS)

    Pratiwi, M.; Ylitervo, P.; Pettersson, A.; Prakoso, T.; Soerawidjaja, T. H.

    2017-06-01

    The fossil oil production could not compensate with the increase of its consumption, because of this reason the renewable alternative energy source is needed to meet this requirement of this fuel. One of the methods to produce hydrocarbon is by decarboxylation of fatty acids. Vegetable oil and fats are the greatest source of fatty acids, so these can be used as raw material for biohydrocarbon production. From other researchers on their past researchs, by heating base soap from divalent metal, those metal salts will decarboxylate and produce hydrocarbon. This study investigate the process and characterization of magnesium soaps from palm stearine by Blachford method. The metal soaps are synthesized by direct reaction of palm stearine and magnesium hydroxide to produce magnesium stearine and magnesium stearine base soaps at 140-180°C and 6-10 bar for 3-6 hours. The operation process which succeed to gain metal soaps is 180°C, 10 bar, for 3-6 hours. These metal soaps are then compared with commercial magnesium stearate. Based on Thermogravimetry Analysis (TGA) results, the decomposition temperature of all the metal soaps were 250°C. Scanning Electron Microscope with Energy Dispersive X-ray (SEM-EDX) analysis have shown the traces of sodium sulphate for magnesium stearate commercial and magnesium hydroxide for both type of magnesium stearine soaps. The analysis results from Microwave Plasma-Atomic Emission Spectrometry (MP-AES) have shown that the magnesium content of magnesium stearine approximate with magnesium stearate commercial and lower compare with magnesium stearine base soaps. These experiments suggest that the presented saponification process method could produced metal soaps comparable with the commercial metal soaps.

  19. Direct extraction of the isovector deformation parameter β(1)2 from the (p, n) reaction of 56Fe

    NASA Astrophysics Data System (ADS)

    Orihara, H.; Murakami, T.; Nishihara, S.; Nakagawa, T.; Maeda, K.; Miura, K.; Ohnuma, H.

    1981-11-01

    The reaction 56Fe(p, n) 56Co leading to the analog of the ground state and the first excited 2 + state of 56Fe has been studied at Ep=20, 28, 32 and35MeV. The direct process dominates at higher energies, thus the direct extraction of the isovector deformation parameter β(1)2 is feasible. It is found that β(1)2 is about three times larger than β(0)2, the isoscalar deformation parameter.

  20. Computational Explorations of Mechanisms and Ligand-Directed Selectivities of Copper-Catalyzed Ullmann-Type Reactions

    PubMed Central

    Jones, Gavin O.; Liu, Peng; Houk, K. N.; Buchwald, Stephen L.

    2010-01-01

    Computational investigations of ligand-directed selectivities in Ullmann-type coupling reactions of methanol and methylamine with iodobenzene by β-diketone- and 1,10-phenanthroline-ligated Cu(I) complexes are reported. Density functional theory (DFT) calculations with several functionals were performed on both the nucleophile formation and aryl halide activation steps of these reactions. The origin of ligand-directed selectivities in N- vs. O-arylation reactions as described in a previous publication (J. Am. Chem. Soc. 2007, 129, 3490–3491) were studied and explained. The selectivities observed experimentally are not derived from initial Cu(I)-nucleophile formation, but from the subsequent steps involving aryl halide activation. The arylation may occur via single-electron transfer (SET) or iodine atom transfer (IAT), depending on the electron-donating ability of the ligand and nucleophile. Mechanisms involving either oxidative addition/reductive elimination or sigma-bond metathesis are disfavored. SET mechanisms are favored in reactions promoted by the β-diketone ligand; N-arylation is predicted to be favored in these cases, in agreement with experimental results. The phenanthroline ligand promotes O-arylation reactions via IAT mechanisms in preference to N-arylation reactions, which occur via SET mechanisms; this result is also in agreement with experimental results. PMID:20387898

  1. Insight into organic reactions from the direct random phase approximation and its corrections

    NASA Astrophysics Data System (ADS)

    Ruzsinszky, Adrienn; Zhang, Igor Ying; Scheffler, Matthias

    2015-10-01

    The performance of the random phase approximation (RPA) and beyond-RPA approximations for the treatment of electron correlation is benchmarked on three different molecular test sets. The test sets are chosen to represent three typical sources of error which can contribute to the failure of most density functional approximations in chemical reactions. The first test set (atomization and n-homodesmotic reactions) offers a gradually increasing balance of error from the chemical environment. The second test set (Diels-Alder reaction cycloaddition = DARC) reflects more the effect of weak dispersion interactions in chemical reactions. Finally, the third test set (self-interaction error 11 = SIE11) represents reactions which are exposed to noticeable self-interaction errors. This work seeks to answer whether any one of the many-body approximations considered here successfully addresses all these challenges.

  2. Direct imaging of covalent bond structure in single-molecule chemical reactions.

    PubMed

    de Oteyza, Dimas G; Gorman, Patrick; Chen, Yen-Chia; Wickenburg, Sebastian; Riss, Alexander; Mowbray, Duncan J; Etkin, Grisha; Pedramrazi, Zahra; Tsai, Hsin-Zon; Rubio, Angel; Crommie, Michael F; Fischer, Felix R

    2013-06-21

    Observing the intricate chemical transformation of an individual molecule as it undergoes a complex reaction is a long-standing challenge in molecular imaging. Advances in scanning probe microscopy now provide the tools to visualize not only the frontier orbitals of chemical reaction partners and products, but their internal covalent bond configurations as well. We used noncontact atomic force microscopy to investigate reaction-induced changes in the detailed internal bond structure of individual oligo-(phenylene-1,2-ethynylenes) on a (100) oriented silver surface as they underwent a series of cyclization processes. Our images reveal the complex surface reaction mechanisms underlying thermally induced cyclization cascades of enediynes. Calculations using ab initio density functional theory provide additional support for the proposed reaction pathways.

  3. Insight into organic reactions from the direct random phase approximation and its corrections

    SciTech Connect

    Ruzsinszky, Adrienn; Zhang, Igor Ying; Scheffler, Matthias

    2015-10-14

    The performance of the random phase approximation (RPA) and beyond-RPA approximations for the treatment of electron correlation is benchmarked on three different molecular test sets. The test sets are chosen to represent three typical sources of error which can contribute to the failure of most density functional approximations in chemical reactions. The first test set (atomization and n-homodesmotic reactions) offers a gradually increasing balance of error from the chemical environment. The second test set (Diels-Alder reaction cycloaddition = DARC) reflects more the effect of weak dispersion interactions in chemical reactions. Finally, the third test set (self-interaction error 11 = SIE11) represents reactions which are exposed to noticeable self-interaction errors. This work seeks to answer whether any one of the many-body approximations considered here successfully addresses all these challenges.

  4. Fundamental studies of retrograde reactions in direct liquefaction. Final report, September 20, 1988--November 20, 1990

    SciTech Connect

    Serio, M.A.; Solomon, P.R.; Kroo, E.; Charpenay, S.; Bassilakis, R.

    1991-12-17

    The overall objective of the program was to improve the understanding of retrograde reactions and their dependencies on coal rank and structure, and/or coal modifications and reaction conditions. Because retrograde reactions are competitive with bond breaking reactions, an understanding of both is required to shift the competition in favor of the latter. Related objectives were to clarify the conflicting observations reported in literature on such major topics as the role of oxygen groups in retrograde reactions and to provide a bridge from very fundamental studies on pure compounds to phenomenological studies on actual coal. This information was integrated into the FG-DVC model, which was improved and extended to the liquefaction context.

  5. Low temperature sintering of PNSZT.

    SciTech Connect

    Young, Amanda L.; Zschiesche, Dale J.; Moore, Roger Howard; Roesler, Alexander William; Hutchinson, Michael Andrew

    2009-01-01

    Pb-based ferroelectrics are useful because of their large dielectric constants, high polarization values, and strong piezoelectric coefficients, but typically require sintering temperatures >1200 C, which leads to loss of the volatile Pb cation and necessitates the use of Pt electrodes for cofired parts. Reduced sintering temperatures can minimize lead loss and enable the use of cheaper electrodes, but must not sacrifice electrical performance. A systematic study of dopants to lower the sintering temperature of PNSZT (Pb0.992 (Zr0.815 Ti0.05 Sn0.135)0.9845 Nb0.155 O3) led to densities greater than 98.5% of theoretical at temperatures as low as 1100 C with as little as 0.2 wt% of a Pb glass additive or as high as 98% at 900 C with Cu2O additions with equivalent electrical properties to undoped materials.

  6. Activity-Directed Synthesis with Intermolecular Reactions: Development of a Fragment into a Range of Androgen Receptor Agonists

    PubMed Central

    Karageorgis, George; Dow, Mark; Aimon, Anthony; Warriner, Stuart; Nelson, Adam

    2015-01-01

    Activity-directed synthesis (ADS), a novel discovery approach in which bioactive molecules emerge in parallel with associated syntheses, was exploited to develop a weakly binding fragment into novel androgen receptor agonists. Harnessing promiscuous intermolecular reactions of carbenoid compounds enabled highly efficient exploration of chemical space. Four substrates were prepared, yet exploited in 326 reactions to explore diverse chemical space; guided by bioactivity alone, the products of just nine of the reactions were purified to reveal diverse novel agonists with up to 125-fold improved activity. Remarkably, one agonist stemmed from a novel enantioselective transformation; this is the first time that an asymmetric reaction has been discovered solely on the basis of the biological activity of the product. It was shown that ADS is a significant addition to the lead generation toolkit, enabling the efficient and rapid discovery of novel, yet synthetically accessible, bioactive chemotypes. PMID:26358926

  7. Low temperature sintering of Ag nanoparticles for flexible electronics packaging

    NASA Astrophysics Data System (ADS)

    Hu, A.; Guo, J. Y.; Alarifi, H.; Patane, G.; Zhou, Y.; Compagnini, G.; Xu, C. X.

    2010-10-01

    We achieve robust bonding of Cu wires to Cu pads on polyimide with silver nanopaste cured at 373 K. The paste is prepared by simply condensing Ag nanoparticle (NP) solution via centrifuging. The bonding is formed by solid state sintering of Ag NPs through neck growth and direct metallic bonding between clean Ag-Cu interfaces. Both experiment and Monte Carlo simulation confirm that the melting point of joint clusters increases during sintering. This creates improved bonds for use at an elevated operating temperature using Ag NPs.

  8. Sintered Lining for Heat-Pipe Evaporator

    NASA Technical Reports Server (NTRS)

    Ernst, D. M.; Eastman, G. Y.

    1985-01-01

    Hotspots eliminated by lining inner wall. Distribution of heat transfer liquid in heat-pipe evaporator improved by lining inner wall with layer of sintered metal. Sintered layer takes place of layer of screen wick formerly sintered or bonded to wall. Since sintered layer always full of liquid, no hotspot of type that previously arose where former screen wick did not fit properly against wall.

  9. Studies of the initial reactions that occur during direct coal liquefaction

    SciTech Connect

    Stohl, F.V.

    1989-01-01

    The objectives of this work are to identify the types of compounds and process conditions that give rise to retrogressive reactions during preconversion processing. Experiments have been performed to evaluate the impacts of temperature, pressure, catalysts, mineral matter, and hydrogen donor on these reactions. Initial studies have been carried out using dibenzyl ether (DBE) because ether linkages represent one type of bonding believed to be present in coal. Previous studies have analyzed the kinetics and mechanism of thermolysis of DBE and have also used DBE to study effects of process variables in coal liquefaction. Results of thermal reactions with DBE have shown that the main reaction products are toluene, benzaldehyde, benzyl alcohol and benzene. In the presence of catalysts such as ZnCl{sub 2}, the product distributions are more complicated and can contain significant amounts of material with higher molecular weights than DBE. 8 refs., 8 figs.

  10. Preparation of functionalized cyclic enol phosphates by halogen-magnesium exchange and directed deprotonation reactions.

    PubMed

    Piller, Fabian M; Bresser, Tomke; Fischer, Markus K R; Knochel, Paul

    2010-07-02

    Cyclic enol phosphates were magnesiated by a halogen/magnesium exchange reaction or deprotonation using TMP-derived magnesium amide bases. The resulting magnesium reagents react readily with a wide range of electrophiles like allyl bromides and acid chlorides or can be used in Pd-catalyzed cross-coupling reactions. Several optically pure enol phosphates were prepared starting from readily available d-(+)-camphor derivatives.

  11. Characterization of polycrystalline cBN compacts sintered without any additives

    NASA Astrophysics Data System (ADS)

    Tan, N.; Liu, C. J.; Li, Y. J.; Dou, Y. W.; Wang, H. K.; Ma, H.; Kou, Z. L.; He, D. W.

    2011-01-01

    Sintered cubic boron nitride (cBN) is widely used in various industrial applications because of its extreme wear and corrosion resistance, thermal and electrical properties. Conventional cBN sintered compacts contain binder materials and the binder materials remarkably affect their mechanical and thermal properties. In this work, polycrystalline cBN (PcBN) compacts were sintered on WC-16 wt.%Co substrates without any sintering agent at static high pressure of 5.0 GPa and temperatures of 1550-1750°C1750circC-> for 3-20 min. Chemical reactions between cBN and substances infiltrated from the substrates occurred during the high pressure and high temperature (HPHT) sintering process. Reaction products and their contents strongly depended on the sintering temperatures and heat treatment times according to the X-ray diffraction (XRD) observations. Scanning electron microscopy (SEM) analysis showed that some samples sintered under some specific conditions had plenty of cBN-to-cBN bonding among cBN grains and homogeneous microstructures. We also found that the formation of the cBN-to-cBN bonding in the samples had given rise to an improvement in cutting performance.

  12. Dislocation generation during early stage sintering.

    NASA Technical Reports Server (NTRS)

    Sheehan, J. E.; Lenel, F. V.; Ansell, G. S.

    1973-01-01

    Discussion of the effects of capillarity-induced stresses on dislocations during early stage sintering. A special version of Hirth's (1963) theoretical calculation procedures modified to describe dislocation nucleation on planes meeting the sintering body's neck surface obliquely is shown to predict plastic flow at stress levels know to exist between micron size metal particles in the early stages of sintering.

  13. Direct experimental probing and theoretical analysis of the reaction between the simplest Criegee intermediate CH 2 OO and isoprene

    DOE PAGES

    Decker, Z. C. J.; Au, K.; Vereecken, L.; ...

    2017-01-01

    Recent advances in the spectroscopy of Criegee intermediates (CI) have enabled direct kinetic studies of these highly reactive chemical species. The impact of CI chemistry is currently being incorporated into atmospheric models, including their reactions with trace organic and inorganic compounds. Isoprene, C5H8, is a doubly-unsaturated hydrocarbon that accounts for the largest share of all biogenic emissions around the globe and is also a building block of larger volatile organic compounds. We report direct measurements of the reaction of the simplest CI (CH2OO) with isoprene, using time-resolved cavity-enhanced UV absorption spectroscopy. We find the reaction to be pressure-independent between 15–100more » Torr, with a rate coefficient that varies from (1.5 ± 0.1) × 10–15 cm3 molecule–1 s–1 at room temperature to (23 ± 2) × 10–15 cm3 molecule–1 s–1 at 540 K. Quantum chemical and transition-state theory calculations of 16 unique channels for CH2OO + isoprene somewhat underpredict the observed T-dependence of the total reaction rate coefficient, but are overall in good agreement with the experimental measurements. Finally, this reaction is broadly similar to those with smaller alkenes, proceeding by 1,3-dipolar cycloaddition to one of the two conjugated double bonds of isoprene.« less

  14. Direct experimental probing and theoretical analysis of the reaction between the simplest Criegee intermediate CH2OO and isoprene

    DOE PAGES

    Decker, Z. C. J.; Au, K.; Vereecken, L.; ...

    2017-03-07

    Recent advances in the spectroscopy of Criegee intermediates (CI) have enabled direct kinetic studies of these highly reactive chemical species. The impact of CI chemistry is currently being incorporated into atmospheric models, including their reactions with trace organic and inorganic compounds. Isoprene, C5H8, is a doubly-unsaturated hydrocarbon that accounts for the largest share of all biogenic emissions around the globe and is also a building block of larger volatile organic compounds. We report direct measurements of the reaction of the simplest CI (CH2OO) with isoprene, using time-resolved cavity-enhanced UV absorption spectroscopy. We find the reaction to be pressure-independent between 15–100more » Torr, with a rate coefficient that varies from (1.5 ± 0.1) × 10–15 cm3 molecule–1 s–1 at room temperature to (23 ± 2) × 10–15 cm3 molecule–1 s–1 at 540 K. Quantum chemical and transition-state theory calculations of 16 unique channels for CH2OO + isoprene somewhat underpredict the observed T-dependence of the total reaction rate coefficient, but are overall in good agreement with the experimental measurements. Finally, this reaction is broadly similar to those with smaller alkenes, proceeding by 1,3-dipolar cycloaddition to one of the two conjugated double bonds of isoprene.« less

  15. Direct experimental probing and theoretical analysis of the reaction between the simplest Criegee intermediate CH2OO and isoprene.

    PubMed

    Decker, Z C J; Au, K; Vereecken, L; Sheps, L

    2017-03-13

    Recent advances in the spectroscopy of Criegee intermediates (CI) have enabled direct kinetic studies of these highly reactive chemical species. The impact of CI chemistry is currently being incorporated into atmospheric models, including their reactions with trace organic and inorganic compounds. Isoprene, C5H8, is a doubly-unsaturated hydrocarbon that accounts for the largest share of all biogenic emissions around the globe and is also a building block of larger volatile organic compounds. We report direct measurements of the reaction of the simplest CI (CH2OO) with isoprene, using time-resolved cavity-enhanced UV absorption spectroscopy. We find the reaction to be pressure-independent between 15-100 Torr, with a rate coefficient that varies from (1.5 ± 0.1) × 10(-15) cm(3) molecule(-1) s(-1) at room temperature to (23 ± 2) × 10(-15) cm(3) molecule(-1) s(-1) at 540 K. Quantum chemical and transition-state theory calculations of 16 unique channels for CH2OO + isoprene somewhat underpredict the observed T-dependence of the total reaction rate coefficient, but are overall in good agreement with the experimental measurements. This reaction is broadly similar to those with smaller alkenes, proceeding by 1,3-dipolar cycloaddition to one of the two conjugated double bonds of isoprene.

  16. Direct Reactions at Relativistic Energies: A New Insight into the Single-Particle Structure of Exotic Nuclei

    NASA Astrophysics Data System (ADS)

    Cortina-Gil, Dolores

    Direct reactions proceed in a single step, allowing to disentangle structural properties of nuclei from the reaction mechanism. The availability of radioactive beams gives rise to a renewed activity in this field enlarging the opportunities to explore the single-particle properties of exotic nuclei. Different kinds of direct reactions have been employed in different energy regimes. At high energies, the removal of one(two)-nucleon(s) (referred to as nucleon knockout in this text) from a fast exotic projectile has been extensively investigated, exploring the nuclear structure of the peripheral tail of wave functions and providing a direct insight into the single-particle properties. More than 25 years of experimental and theoretical work will be reviewed in this lecture. This exploration has recently been rejuvenated with the possibility of quasi-free scattering applied to rare isotopes. This method will be a substantial part of the program of future experimental facilities, with the results of pilot experiments now coming to light. Quasi-free scattering will complement the information gained with nucleon knockout studies, exploring deeper regions in the wave function and allowing the determination of spectral functions for both weakly and deeply bound nucleons. This lecture provides a general overview of the experimental achievements reached so far using both complementary techniques. A brief introduction to the reaction mechanisms and a simplified interpretation of the observables obtained will be presented.

  17. Effect of milling and leaching on the structure of sintered silicon

    NASA Technical Reports Server (NTRS)

    Yeh, H. C.; Glascow, T. K.; Herbell, T. P.

    1980-01-01

    Sintering was performed in He for 16 hours at 1200, 1250, and 1300 C. Compacts of as-received Si did not densify during sintering. Milling reduced the average particle size to below 0.5 micrometer and enhanced densification (1.75 g/cc). Leaching milled Si further enhanced densification (1.90 g/cc max.) and decreased structural coarsening. After sintering, the structure of the milled and leached powder compacts appears favorable for the production of reaction bonded silicon nitride.

  18. Densification and Electrical Properties of Zinc Oxide Varistors Microwave-Sintered Under Different Oxygen Partial Pressures

    NASA Astrophysics Data System (ADS)

    Lin, Cong; Wang, Bo; Xu, Zheng; Peng, Hu

    2012-11-01

    ZnO varistors were prepared by microwave sintering under different oxygen partial pressures. The temperature profile and the densification behavior in different atmospheres were investigated. It was found that the density of ZnO varistors during sintering was the key factor affecting the absorption of microwave energy. The electrical properties, including the nonlinear properties and capacitance-voltage ( C- V) characteristics, were also carefully studied. The results showed that the oxygen partial pressure has significant effects on the electrical properties of ZnO varistors by changing the concentration of defects through a series of reactions involving oxygen during sintering.

  19. Dynamic Reaction Mechanisms of ClO(-) with CH3Cl: Comparison Between Direct Dynamics Trajectory Simulations and Experiment.

    PubMed

    Yu, Feng

    2016-03-24

    We have investigated the dynamic reaction mechanisms of *ClO¯ with CH3Cl (the asterisk is utilized to label a different Cl atom). Ab initio molecular dynamics simulations at the MP2/6-31+G(d,p) level of theory have been employed to compute the dynamic trajectories. On the basis of our simulations, the dynamic reaction pathways for the bimolecular nucleophilic substitution (SN2) reaction channel and SN2-induced elimination reaction channel are clearly illustrated. For the SN2 reaction channel, some trajectories directly dissociate to the final products of CH3O*Cl and Cl¯, whereas the others involve the dynamic Cl¯···CH3O*Cl intermediate complex. As to the SN2-induced elimination reaction channel, the trajectories lead to the final products of CH2O, HCl, and *Cl¯ through the dynamic Cl¯···CH3O*Cl intermediate complex. More significantly, the product branching ratios of Cl¯ and *Cl¯ predicted by our simulations are basically consistent with previous experimental results (Villano et al. J. Am. Chem. Soc. 2009, 131, 8227-8233).

  20. Sintering additives for zirconia ceramics

    SciTech Connect

    Wu, S.

    1986-01-01

    This book is an overview of sintering science and its application to zirconia materials including CaO, MgO, and Y/sub 2/O/sub 3/-CeO/sub 2/ doped materials. This book is a reference for first-time exposure to zirconia materials technology, particularly densification.

  1. Sintering of polydisperse viscous droplets

    NASA Astrophysics Data System (ADS)

    Wadsworth, Fabian B.; Vasseur, Jérémie; Llewellin, Edward W.; Dingwell, Donald B.

    2017-03-01

    Sintering—or coalescence—of compacts of viscous droplets is driven by the interfacial tension between the droplets and the interstitial gas phase. The process, which occurs in a range of industrial and natural settings, such as the manufacture of ceramics and the welding of volcanic ash, causes the compact to densify, to become stronger, and to become less permeable. We investigate the role of droplet polydispersivity in sintering dynamics by conducting experiments in which populations of glass spheres with different size distributions are heated to temperatures above the glass transition interval. We quantify the progress of sintering by tracking changes in porosity with time. The sintering dynamics is modeled by treating the system as a random distribution of interstitial gas bubbles shrinking under the action of interfacial tension only. We identify the scaling between the polydispersivity of the initial droplets and the dynamics of bulk densification. The framework that we develop allows the sintering dynamics of arbitrary polydisperse populations of droplets to be predicted if the initial droplet (or particle) size distribution is known.

  2. SINTERING OF NASCENT CALCIUM OXIDE

    EPA Science Inventory

    The paper discusses the measurement of the sintering rate of CaO in a nitrogen atmosphere at temperatures of 700-1100 C. CaO prepared from ultrapure CaCO3 was compared with an impure CaO derived from limestone. Both materials yielded an initial surface area of 104 sq m/g. The rat...

  3. SINTERING OF NASCENT CALCIUM OXIDE

    EPA Science Inventory

    The paper discusses the measurement of the sintering rate of CaO in a nitrogen atmosphere at temperatures of 700-1100 C. CaO prepared from ultrapure CaCO3 was compared with an impure CaO derived from limestone. Both materials yielded an initial surface area of 104 sq m/g. The rat...

  4. Microwave sintering of boron carbide

    DOEpatents

    Blake, R.D.; Katz, J.D.; Petrovic, J.J.; Sheinberg, H.

    1988-06-10

    A method for forming boron carbide into a particular shape and densifying the green boron carbide shape. Boron carbide in powder form is pressed into a green shape and then sintered, using a microwave oven, to obtain a dense boron carbide body. Densities of greater than 95% of theoretical density have been obtained. 1 tab.

  5. Palladium-Catalyzed Reactions of Arylindium Reagents Prepared Directly from Aryl Iodides and Indium Metal

    PubMed Central

    Papoian, Vardan

    2008-01-01

    Treatment of aryl iodides with indium metal in the presence of lithium chloride leads to the formation of an organoindium reagent capable of participating in cross-coupling reactions under transition-metal catalysis. Combination with aryl halides in the presence of 5 mol% Cl2Pd(dppf) furnishes biaryl compounds in good yields; similarly, reaction with acyl halides or allylic acetates/carbonates in the presence of 5–10 mol % palladium catalyst leads to arylketones and allylic substitution products, respectively, in moderate yields. The reactions are tolerant of the presence of protic solvents, and ~85% of the indium metal employed can be recovered by reduction of the residual indium salts with zinc(0). PMID:18722408

  6. Direct conversion from Jerusalem artichoke to hydroxymethylfurfural (HMF) using the Fenton reaction.

    PubMed

    Seo, Yeong Hwan; Han, Jong-In

    2014-05-15

    A simple method for hydroxymethylfurfural (HMF) production from non-crop biomass of the Jerusalem artichoke was developed using the Fenton reaction, in a mixture of 2-butanol and water. Four parameters (temperature, reaction time, Fe(2+) concentration, and H2O2 concentration) were identified as experimental factors, and HMF yield was selected as the response parameter. The experimental factors were optimised by employing Response Surface Methodology (RSM). The maximum HMF yield, of 46%, was obtained with a reaction time of 90 min, Fe(2+) concentration of 1.3 mM, and 0.47 M of H2O2 at 180 °C. Copyright © 2014. Published by Elsevier Ltd.

  7. REUSABLE REACTION VESSEL

    DOEpatents

    Soine, T.S.

    1963-02-26

    This patent shows a reusable reaction vessel for such high temperature reactions as the reduction of actinide metal chlorides by calcium metal. The vessel consists of an outer metal shell, an inner container of refractory material such as sintered magnesia, and between these, a bed of loose refractory material impregnated with thermally conductive inorganic salts. (AEC)

  8. Pressure-assisted low-temperature sintering for paper-based writing electronics.

    PubMed

    Xu, L Y; Yang, G Y; Jing, H Y; Wei, J; Han, Y D

    2013-09-06

    With the aim of preparing paper-based writing electronics, a kind of conductive pen was made with nano-silver ink as the conductive component and a rollerball pen as the writing implement. This was used to direct-write conductive patterns on Epson photo paper. In order to decrease the sintering temperature, pressure was introduced to enhance the driving forces for sintering. Compared with hot sintering without pressure, hot-pressure can effectively improve the conductivity of silver coatings, reduce the sintering time and thus improve productivity. Importantly, pressure can achieve a more uniform and denser microstructure, which increases the connection strength of the silver coating. At the optimum hot-pressure condition (sintering temperature 120 ° C/sintering pressure 25 MPa/sintering time 15 min), a typical measured resistivity value was 1.43 × 10⁻⁷ Ω m, nine greater than that of bulk silver. This heat treatment process is compatible with paper and does not cause any damage to the paper substrates. Even after several thousand bending cycles, the resistivity values of writing tracks by hot-pressure sintering stay almost the same (from 1.43 × 10⁻⁷ to 1.57 × 10⁻⁷ Ω m). The stability and flexibility of the writing circuits are good, which demonstrates the promising future of writing electronics.

  9. Flash (Ultra-Rapid) Spark-Plasma Sintering of Silicon Carbide

    NASA Astrophysics Data System (ADS)

    Olevsky, Eugene A.; Rolfing, Stephen M.; Maximenko, Andrey L.

    2016-09-01

    A new ultra-rapid process of flash spark plasma sintering is developed. The idea of flash spark plasma sintering (or flash hot pressing - FHP) stems from the conducted theoretical analysis of the role of thermal runaway phenomena for material processing by flash sintering. The major purpose of the present study is to theoretically analyze the thermal runaway nature of flash sintering and to experimentally address the challenge of uncontrollable thermal conditions by the stabilization of the flash sintering process through the application of the external pressure. The effectiveness of the developed FHP technique is demonstrated by the few seconds–long consolidation of SiC powder in an industrial spark plasma sintering device. Specially designed sacrificial dies heat the pre-compacted SiC powder specimens to a critical temperature before applying any voltage to the powder volume and allowing the electrode-punches of the SPS device setup to contact the specimens and pass electric current through them under elevated temperatures. The experimental results demonstrate that flash sintering phenomena can be realized using conventional SPS devices. The usage of hybrid heating SPS devices is pointed out as the mainstream direction for the future studies and utilization of the new flash hot pressing (ultra-rapid spark plasma sintering) technique.

  10. Hot-spring sinter deposits in the Alvord-Pueblo Valley, Harney County, Oregon

    SciTech Connect

    Cummings, M.L.; St. John, A.M. . Dept. of Geology)

    1993-04-01

    Silica sinter deposits occur at Borax Lake, Alvord Hot Springs, and Mickey Springs in the Alvord-Pueblo Valley. Although the sinter deposits occur in areas of active hot springs, sinter is not being deposited. Hot springs are localized along faults that have been active since the Pleistocene. The sinter deposits formed after the drying of glacial Lake Alvord, but before and during extensive wind deflation of glacial-lacustrine sediments. At Mickey Springs, sinter rests directly on unaltered, unconsolidated lithic-rich sand. At Borax Lake, sinter overlies unaltered diatomite, but some armoring, presumably by silica, of the 30 m vent has developed. Field relations suggest rapid dumping of silica from solution without alteration of the country rock at the vent. Discharge of thermal fluids and cold groundwater along the same structure may have produced colloidal silica carried in a solution stripped of dissolved silica. Sinter is composed of opal-a, traces of detrital feldspar and quartz, and evaporation-related boracite. The concentration of Sb is similar among the three sinter deposits (20 to 70 ppm); however, As, Cs, and Br are highest at Borax Lake (5 to 560 ppm; 26 to 118 ppm; 5 to 1,040 ppm) while Hg is highest at Mickey Springs (1.0 to 5.2 ppm).

  11. Mechanistic evaluation of the effect of sintering on Compritol 888 ATO matrices.

    PubMed

    Rao, Monica; Ranpise, Anuradha; Borate, Sameer; Thanki, Kaushik

    2009-01-01

    The present research studied the effect of sintering technique in the development of a controlled release formulation for ketorolac tromethamine. The method consisted of mixing drug and wax powder (Compritol 888 ATO) along with lactose as diluent and talc as lubricant followed by direct compression at room temperature. The compressed fluffy matrices were kept at 80 degrees C for 1, 2, and 3 h for sintering. The sintered tablets were characterized by their physical parameters and in vitro dissolution profile. The sintering time markedly affected the drug release properties of Compritol 888 ATO matrices. It is notable that the release rate of ketorolac tromethamine from matrices was inversely related to the time of sintering. This may be due to the increase in the extent and firmness of sintering which further compacts the mass so that drug release is affected. Contact angle measurement and scanning electron microscopy analysis indicated that heat treatment caused the wax to melt and redistribute. This redistributed wax formed a network-like structure in which the drug along with lactose is entrapped. This particular formed matrix is responsible for retarding the drug release. Fourier transform infrared spectroscopy results did not show any drug-wax interaction due to sintering. Differential scanning calorimetric and powder X-ray diffraction studies ruled out the occurrence of solid solution and polymorphic changes of the drug. Drug release from the wax tablets with or without sintering was best described by the Higuchi equation.

  12. Flash (Ultra-Rapid) Spark-Plasma Sintering of Silicon Carbide

    PubMed Central

    Olevsky, Eugene A.; Rolfing, Stephen M.; Maximenko, Andrey L.

    2016-01-01

    A new ultra-rapid process of flash spark plasma sintering is developed. The idea of flash spark plasma sintering (or flash hot pressing - FHP) stems from the conducted theoretical analysis of the role of thermal runaway phenomena for material processing by flash sintering. The major purpose of the present study is to theoretically analyze the thermal runaway nature of flash sintering and to experimentally address the challenge of uncontrollable thermal conditions by the stabilization of the flash sintering process through the application of the external pressure. The effectiveness of the developed FHP technique is demonstrated by the few seconds–long consolidation of SiC powder in an industrial spark plasma sintering device. Specially designed sacrificial dies heat the pre-compacted SiC powder specimens to a critical temperature before applying any voltage to the powder volume and allowing the electrode-punches of the SPS device setup to contact the specimens and pass electric current through them under elevated temperatures. The experimental results demonstrate that flash sintering phenomena can be realized using conventional SPS devices. The usage of hybrid heating SPS devices is pointed out as the mainstream direction for the future studies and utilization of the new flash hot pressing (ultra-rapid spark plasma sintering) technique. PMID:27624641

  13. Flash (Ultra-Rapid) Spark-Plasma Sintering of Silicon Carbide.

    PubMed

    Olevsky, Eugene A; Rolfing, Stephen M; Maximenko, Andrey L

    2016-09-14

    A new ultra-rapid process of flash spark plasma sintering is developed. The idea of flash spark plasma sintering (or flash hot pressing - FHP) stems from the conducted theoretical analysis of the role of thermal runaway phenomena for material processing by flash sintering. The major purpose of the present study is to theoretically analyze the thermal runaway nature of flash sintering and to experimentally address the challenge of uncontrollable thermal conditions by the stabilization of the flash sintering process through the application of the external pressure. The effectiveness of the developed FHP technique is demonstrated by the few seconds-long consolidation of SiC powder in an industrial spark plasma sintering device. Specially designed sacrificial dies heat the pre-compacted SiC powder specimens to a critical temperature before applying any voltage to the powder volume and allowing the electrode-punches of the SPS device setup to contact the specimens and pass electric current through them under elevated temperatures. The experimental results demonstrate that flash sintering phenomena can be realized using conventional SPS devices. The usage of hybrid heating SPS devices is pointed out as the mainstream direction for the future studies and utilization of the new flash hot pressing (ultra-rapid spark plasma sintering) technique.

  14. Pressure-assisted low-temperature sintering for paper-based writing electronics

    NASA Astrophysics Data System (ADS)

    Y Xu, L.; Y Yang, G.; Y Jing, H.; Wei, J.; Han, Y. D.

    2013-09-01

    With the aim of preparing paper-based writing electronics, a kind of conductive pen was made with nano-silver ink as the conductive component and a rollerball pen as the writing implement. This was used to direct-write conductive patterns on Epson photo paper. In order to decrease the sintering temperature, pressure was introduced to enhance the driving forces for sintering. Compared with hot sintering without pressure, hot-pressure can effectively improve the conductivity of silver coatings, reduce the sintering time and thus improve productivity. Importantly, pressure can achieve a more uniform and denser microstructure, which increases the connection strength of the silver coating. At the optimum hot-pressure condition (sintering temperature 120 ° C/sintering pressure 25 MPa/sintering time 15 min), a typical measured resistivity value was 1.43 × 10-7 Ω m, nine greater than that of bulk silver. This heat treatment process is compatible with paper and does not cause any damage to the paper substrates. Even after several thousand bending cycles, the resistivity values of writing tracks by hot-pressure sintering stay almost the same (from 1.43 × 10-7 to 1.57 × 10-7 Ω m). The stability and flexibility of the writing circuits are good, which demonstrates the promising future of writing electronics.

  15. Direct Measurements of Unimolecular and Bimolecular Reaction Kinetics of the Criegee Intermediate (CH3)2COO.

    PubMed

    Chhantyal-Pun, Rabi; Welz, Oliver; Savee, John D; Eskola, Arkke J; Lee, Edmond P F; Blacker, Lucy; Hill, Henry R; Ashcroft, Matilda; Khan, M Anwar H; Lloyd-Jones, Guy C; Evans, Louise; Rotavera, Brandon; Huang, Haifeng; Osborn, David L; Mok, Daniel K W; Dyke, John M; Shallcross, Dudley E; Percival, Carl J; Orr-Ewing, Andrew J; Taatjes, Craig A

    2017-01-12

    The Criegee intermediate acetone oxide, (CH3)2COO, is formed by laser photolysis of 2,2-diiodopropane in the presence of O2 and characterized by synchrotron photoionization mass spectrometry and by cavity ring-down ultraviolet absorption spectroscopy. The rate coefficient of the reaction of the Criegee intermediate with SO2 was measured using photoionization mass spectrometry and pseudo-first-order methods to be (7.3 ± 0.5) × 10(-11) cm(3) s(-1) at 298 K and 4 Torr and (1.5 ± 0.5) × 10(-10) cm(3) s(-1) at 298 K and 10 Torr (He buffer). These values are similar to directly measured rate coefficients of anti-CH3CHOO with SO2, and in good agreement with recent UV absorption measurements. The measurement of this reaction at 293 K and slightly higher pressures (between 10 and 100 Torr) in N2 from cavity ring-down decay of the ultraviolet absorption of (CH3)2COO yielded even larger rate coefficients, in the range (1.84 ± 0.12) × 10(-10) to (2.29 ± 0.08) × 10(-10) cm(3) s(-1). Photoionization mass spectrometry measurements with deuterated acetone oxide at 4 Torr show an inverse deuterium kinetic isotope effect, kH/kD = (0.53 ± 0.06), for reactions with SO2, which may be consistent with recent suggestions that the formation of an association complex affects the rate coefficient. The reaction of (CD3)2COO with NO2 has a rate coefficient at 298 K and 4 Torr of (2.1 ± 0.5) × 10(-12) cm(3) s(-1) (measured with photoionization mass spectrometry), again similar to rate for the reaction of anti-CH3CHOO with NO2. Cavity ring-down measurements of the acetone oxide removal without added reagents display a combination of first- and second-order decay kinetics, which can be deconvolved to derive values for both the self-reaction of (CH3)2COO and its unimolecular thermal decay. The inferred unimolecular decay rate coefficient at 293 K, (305 ± 70) s(-1), is similar to determinations from ozonolysis. The present measurements confirm the large rate coefficient for reaction of

  16. Gravitational Role in Liquid Phase Sintering

    NASA Technical Reports Server (NTRS)

    Upadhyaya, Anish; Iacocca, Ronald G.; German, Randall M.

    1998-01-01

    To comprehensively understand the gravitational effects on the evolution of both the microstructure and the macrostructure during liquid phase sintering, W-Ni-Fe alloys with W content varying from 35 to 98 wt.% were sintered in microgravity. Compositions that slump during ground-based sintering also distort when sintered under microgravity. In ground-based sintering, low solid content alloys distort with a typical elephant-foot profile, while in microgravity, the compacts tend to spheroidize. This study shows that microstructural segregation occurs in both ground-based as well as microgravity sintering. In ground-based experiments, because of the density difference between the solid and the liquid phase, the solid content increases from top to the bottom of the sample. In microgravity, the solid content increases from periphery to the center of the samples. This study also shows that the pores during microgravity sintering act as a stable phase and attain anomalous shapes.

  17. Cold press sintering of simulated lunar basalt

    NASA Technical Reports Server (NTRS)

    Altemir, D. A.

    1993-01-01

    In order to predict the conditions for which the lunar regolith may be adequately sintered, experiments were conducted in which samples of simulated lunar basalt (MLS-1) were pressed at high pressures and then heated in an electric furnace. This sintering process may be referred to as cold press sintering since the material is pressed at room temperature. Although test articles were produced which possessed compressive strengths comparable to that of terrestrial concrete, the cold press sintering process requires very high press pressures and sintering temperatures in order to achieve that strength. Additionally, the prospect of poor internal heat transfer adversely affecting the quality of sintered lunar material is a major concern. Therefore, it is concluded that cold press sintering will most likely be undesirable for the production of lunar construction materials.

  18. Photophysical Study of a Series of Cyanines Part III. The Direct Photooxidation Reaction

    NASA Astrophysics Data System (ADS)

    Lepaja, Shukri; Strub, Henry; Lougnot, Daniel-Joseph

    1983-01-01

    The main degradative pathway of tricarbocyanine dyes in aerated solutions is demonstrated to be a photooxidation; using sensitization techniques and specific quenchers, this reaction is established to proceed via singlet oxygen for a part, and the site at which this species attacks the polymethinic skeleton is unambiguously determined. The major photoproduct is identified as being 1,3,3-trimethyl-2-indolinone.

  19. Chitosan aerogel: a recyclable, heterogeneous organocatalyst for the asymmetric direct aldol reaction in water.

    PubMed

    Ricci, Alfredo; Bernardi, Luca; Gioia, Claudio; Vierucci, Simone; Robitzer, Mike; Quignard, Françoise

    2010-09-14

    Aerogel microspheres of chitosan, an abundant biopolymer obtained from marine crustaceans, have been successfully applied to catalyze the asymmetric aldol reaction in water, providing the products in high yields and with good stereoselectivity (up to 93% ee) and recyclability (up to 4 runs). Yields were favourably affected by additives such as DNP and stearic acid.

  20. Zeolite-directed cascade reactions: cycliacyarylation versus decarboxyarylation of alpha,beta-unsaturated carboxylic acids.

    PubMed

    Chassaing, Stefan; Kumarraja, Mayilvasagam; Pale, Patrick; Sommer, Jean

    2007-09-27

    The interaction of alpha,beta-unsaturated carboxylic acids with benzene derivatives was investigated in H-zeolites and led to two distinct but competing processes, cycliacyarylation and decarboxyarylation. Interestingly, H-USY selectively induced the cycliacyarylation cascade reaction, whereas H-ZSM5 selectively promoted the decarboxyarylation cascade.

  1. Melt Absorbability of Iron Ore Nuclei and Its Influence on Suitable Liquid Content of Sintered Body

    NASA Astrophysics Data System (ADS)

    Wu, Sheng-Li; Su, Bo; Qi, Yuan-Hong; Kou, Ming-Yin; Li, Yuan; Zhang, Wei-Li

    2017-10-01

    Sinter quasi-particles consist of nuclei particles and adhering fines. Therefore, reaction properties of the nuclei ore will ultimately affect the bonding strength of the sintered body. In this study, micro-sintering tests were conducted to explore the melt absorbability of nuclei ore and its effect on the suitable liquid content of the sintered body. The results showed that the melt absorbability is negatively correlated with the lowest assimilation temperature, and the most important mineralogy factor influencing melt absorbability is iron mineral type. The reaction behaviors of melts containing SiO2 or Al2O3 substrates are different, and the reaction process of the melt containing SiO2 is more complicated. In addition, the bonding strength of the sintered body is collectively determined by the liquid phase fluidity of adhering fines and the assimilability of nuclei ore. The high melt absorbability has an adverse effect on bonding strength, and it requires adhering fines to provide more primary melts to meet the requirements for sintered body bonding strength. In the condition with the same liquid content, for nuclei ore with stronger melt absorbability, an appropriate increase in the adhering fines ratio and reduction in segregation basicity are more conducive to improving the bonding strength.

  2. The First Example of Nickel-Catalyzed Silyl-Heck Reactions: Direct Activation of Silyl Triflates Without Iodide Additives

    PubMed Central

    McAtee, Jesse R.; Martin, Sara E. S.; Cinderella, Andrew P.; Reid, William B.; Johnson, Keywan A.

    2014-01-01

    For the first time, nickel-catalyzed silyl-Heck reactions are reported. Using simple phosphine-supported nickel catalysts, direct activation of silyl triflates has been achieved. These results contrast earlier palladium-catalyzed systems, which require iodide additives to activate silyl-triflates. These nickel-based catalysts exhibit good functional group tolerance in the preparation of vinyl silanes, and unlike earlier systems, allows for the incorporation of trialkylsilanes larger than Me3Si. PMID:24914247

  3. Improvement of the Sintered Surface and Bulk of the Product Via Differentiating Laser Sintering (Melting) Modes

    NASA Astrophysics Data System (ADS)

    Saprykina, N. A.; Saprykin, A. A.; Arkhipova, D. A.; Borovikov, I. F.

    2016-08-01

    Selective laser sintering (melting) enables using metal powdered materials to manufacture products of any geometrical complexity, requiring no preliminary costs to prepare processing equipment. However, quality of the sintered surface is often inadequate as against the product manufactured traditionally. Manufacturing a high quality product requires solution of such vital task as prediction of the sintered surface roughness. The authors address to the effect of laser sintering modes on roughness of the surface, sintered of copper powdered material PMS-l (IIMC-1). The dependence of roughness of the surface layer sintered of copper powder material PMS-l upon sintering process conditions is expressed mathematically. The authors suggest differentiating sintering modes to improve the sintered surface and the bulk of the product and dividing them into rough, semi-finishing, and finishing ones.

  4. Direct observation of redox reactions in Candida parapsilosis ATCC 7330 by Confocal microscopic studies

    PubMed Central

    Venkataraman, Sowmyalakshmi; Narayan, Shoba; Chadha, Anju

    2016-01-01

    Confocal microscopic studies with the resting cells of yeast, Candida parapsilosis ATCC 7330, a reportedly versatile biocatalyst for redox enzyme mediated preparation of optically pure secondary alcohols in high optical purities [enantiomeric excess (ee) up to >99%] and yields, revealed that the yeast cells had large vacuoles under the experimental conditions studied where the redox reaction takes place. A novel fluorescence method was developed using 1-(6-methoxynaphthalen-2-yl)ethanol to track the site of biotransformation within the cells. This alcohol, itself non-fluorescent, gets oxidized to produce a fluorescent ketone, 1-(6-methoxynaphthalen-2-yl)ethanone. Kinetic studies showed that the reaction occurs spontaneously and the products get released out of the cells in less time [5 mins]. The biotransformation was validated using HPLC. PMID:27739423

  5. Reaction Ensemble Molecular Dynamics: Direct Simulation of the Dynamic Equilibrium Properties of Chemically Reacting Mixtures

    DTIC Science & Technology

    2006-09-01

    Therefore, dynamic quantities of reaction mixtures such as the velocity autocorrelation functions and the diffusion coefficients can be accurately...using the virial expression [25]. A standard NVT molecular dynamics method was em- ployed with the equations of motion solved using the Verlet leapfrog...configurational energy, pressure, and species concen- trations) are compared to quantities calculated by the RxMC approach. Second , the dynamic quantities

  6. Acid-Base Pairs in Lewis Acidic Zeolites Promote Direct Aldol Reactions by Soft Enolization.

    PubMed

    Lewis, Jennifer D; Van de Vyver, Stijn; Román-Leshkov, Yuriy

    2015-08-17

    Hf-, Sn-, and Zr-Beta zeolites catalyze the cross-aldol condensation of aromatic aldehydes with acetone under mild reaction conditions with near quantitative yields. NMR studies with isotopically labeled molecules confirm that acid-base pairs in the Si-O-M framework ensemble promote soft enolization through α-proton abstraction. The Lewis acidic zeolites maintain activity in the presence of water and, unlike traditional base catalysts, in acidic solutions.

  7. Direct site-selective arylation of enamides via a decarboxylative cross-coupling reaction.

    PubMed

    Gigant, Nicolas; Chausset-Boissarie, Laëtitia; Gillaizeau, Isabelle

    2013-02-15

    An efficient Pd-catalyzed decarboxylative cross-coupling reaction of simple enamides was achieved. Depending on the choice of the nitrogen-protecting group, a site-selective synthesis of mono- or diarylated framework(s) was performed under mild conditions. This unprecedented reactivity could be applied to the synthesis of a range of 2- or 2,4-diarylated nitrogen-containing bioactive derivatives.

  8. Sinter-vein correlations at Buckskin Mountain, National district, Humboldt County, Nevada

    USGS Publications Warehouse

    Vikre, P.G.

    2007-01-01

    in veins and sinter. Acid-sulfate fluid of the second fluid regime was derived from oxidation of H2S and other volatiles exsolved from sinter-vein fluid. Acid-sulfate fluid produced (1) a subhorizontal zone of partially leached basinal deposits and rhyolite from the paleosurface to a depth of ???60 m, and (2) laterally pervasive zones, ???100 to 200 m thick, of quartz + alunite ?? hematite and quartz + kaolinite + pyrite in volcaniclastic deposits immediately beneath partially leached rocks, but this fluid did not decompose selenide-sulfide-precious metal phases in sinter. Paragenetically late vein and wall-rock assemblages, including marcasite + pyrite, calcite, and kaolinite-replaced K minerals, record deeper transition of sinter-vein fluid into acid-sulfate fluid in vein conduits. This transition occurred as regional subsidence, manifested by the Goosey Lake depression immediately east of Buckskin Mountain, lowered the pieziometric surface at Buckskin Mountain, terminated sinter deposition, and caused boiling and/or degassing of sinter-vein fluid. The timing of subsidence is recorded by a decrease in alunite ages, from ca. 15.8 to 15.6 Ma, with depth below sinter. Lateral replacement of sinter and partially leached epiclastic deposits and rhyolite by opal-A marks the termination of the two hydrothermal regimes that lasted ???0.5 m.y. and followed rhyolitic volcanism of similar duration. Veins and sinter display textures that attest to plastic deformation, spalling, and gravitational settling, and indicate fluid-flow direction, velocity, and density stratification which, with conduit topology, may have influenced precious metal tenor in the veins. Components of sinter and veins were transported as colloids, formed in supersaturated sinter-vein fluid, that aggregated or coagulated as incompetent gelatinous layers in shallow pools and in underlying, near-vertical conduits in rhyolite and initially crystallized as opal and chalcedony. The low thermal conductivity of

  9. Direct observation of ultrafast-electron-transfer reactions unravels high effectiveness of reductive DNA damage

    PubMed Central

    Nguyen, Jenny; Ma, Yuhan; Luo, Ting; Bristow, Robert G.; Jaffray, David A.; Lu, Qing-Bin

    2011-01-01

    Both water and electron-transfer reactions play important roles in chemistry, physics, biology, and the environment. Oxidative DNA damage is a well-known mechanism, whereas the relative role of reductive DNA damage is unknown. The prehydrated electron (), a novel species of electrons in water, is a fascinating species due to its fundamental importance in chemistry, biology, and the environment. is an ideal agent to observe reductive DNA damage. Here, we report both the first in situ femtosecond time-resolved laser spectroscopy measurements of ultrafast-electron-transfer (UET) reactions of with various scavengers (KNO3, isopropanol, and dimethyl sulfoxide) and the first gel electrophoresis measurements of DNA strand breaks induced by and OH• radicals co-produced by two-UV-photon photolysis of water. We strikingly found that the yield of reductive DNA strand breaks induced by each is twice the yield of oxidative DNA strand breaks induced by each OH• radical. Our results not only unravel the long-standing mystery about the relative role of radicals in inducing DNA damage under ionizing radiation, but also challenge the conventional notion that oxidative damage is the main pathway for DNA damage. The results also show the potential of femtomedicine as a new transdisciplinary frontier and the broad significance of UET reactions of in many processes in chemistry, physics, biology, and the environment. PMID:21730183

  10. Children's direct fright and worry reactions to violence in fiction and news television programs.

    PubMed

    van der Molen, Juliette H Walma; Bushman, Brad J

    2008-09-01

    To examine whether violence in fictional and news television content frightens and worries children. Mixed factorial. Type of reaction (fright, worry) and television programming (violent news, violent fiction) were within-subjects factors, whereas age, sex, and television viewing frequency were between-subjects factors. Participants included 572 children (47% boys), aged 8 to 12 years, from 9 urban and rural primary schools in the Netherlands. The main exposure was to descriptions of 8 threats frequently depicted in fictional and news programs (eg, murder, war, house fires). Children reported whether they were frightened or worried by these threats. Violent threats increased both fright and worry. These 2 reactions could be distinguished from one another in a factor analysis. When violent content was described as news, it produced more fear reactions than when it was described as fiction. Fright and worry were greater in girls than in boys, in younger children than in older children, and in light television viewers than in heavy television viewers. Pediatricians should inform parents, educators, policy makers, and broadcasters about the potentially harmful effect of violent programming on children's emotions, especially in the case of news programming.

  11. Direct observation of ultrafast-electron-transfer reactions unravels high effectiveness of reductive DNA damage.

    PubMed

    Nguyen, Jenny; Ma, Yuhan; Luo, Ting; Bristow, Robert G; Jaffray, David A; Lu, Qing-Bin

    2011-07-19

    Both water and electron-transfer reactions play important roles in chemistry, physics, biology, and the environment. Oxidative DNA damage is a well-known mechanism, whereas the relative role of reductive DNA damage is unknown. The prehydrated electron (e(pre)-), a novel species of electrons in water, is a fascinating species due to its fundamental importance in chemistry, biology, and the environment. e(pre)- is an ideal agent to observe reductive DNA damage. Here, we report both the first in situ femtosecond time-resolved laser spectroscopy measurements of ultrafast-electron-transfer (UET) reactions of e(pre)- with various scavengers (KNO(3), isopropanol, and dimethyl sulfoxide) and the first gel electrophoresis measurements of DNA strand breaks induced by e(pre)- and OH(•) radicals co-produced by two-UV-photon photolysis of water. We strikingly found that the yield of reductive DNA strand breaks induced by each e(pre)- is twice the yield of oxidative DNA strand breaks induced by each OH(•) radical. Our results not only unravel the long-standing mystery about the relative role of radicals in inducing DNA damage under ionizing radiation, but also challenge the conventional notion that oxidative damage is the main pathway for DNA damage. The results also show the potential of femtomedicine as a new transdisciplinary frontier and the broad significance of UET reactions of e(pre)- in many processes in chemistry, physics, biology, and the environment.

  12. Asymmetric synthesis of dihydropyranones from ynones by sequential copper(I)-catalyzed direct aldol and silver(I)-catalyzed oxy-Michael reactions.

    PubMed

    Shi, Shi-Liang; Kanai, Motomu; Shibasaki, Masakatsu

    2012-04-16

    Ynones as diene surrogates: the asymmetric synthesis of enantiomerically enriched substituted dihydropyranones is described. The products are obtained in two steps by a copper(I)-catalyzed direct aldol reaction of ynones followed by a silver-catalyzed oxy-Michael reaction. This easy method is compatible with both aromatic and aliphatic substrates, and provides excellent chemoselectivity under mild reaction conditions.

  13. Microwave sintering studies on low loss (Zn, Mg)TiO3 dielectric resonator materials.

    PubMed

    Sirugudu, Roopas Kiran; Vemuri, Rama Krishna Murthy; Murty, B S

    2013-01-01

    Low dielectric loss Zn07Mg0.3TiO3 and MgTiO3 microwave dielectric resonators were prepared by the conventional solid state reaction method. The microwave interaction with these materials has been studied using both single-mode and multimode microwave furnaces operating at a frequency of 2.45 GHz. Microwave sintering could be achieved using a multimode microwave furnace only, whereas, interaction with a single-mode furnace showed plasma generation. Phase formation was observed by X-ray diffraction. Microwave dielectric characteristics such as dielectric constant (epsilon'), quality factor (Q x f) and temperature coefficient of resonant frequency (tauf) of microwave sintered samples were measured using a vector network analyzer and compared with conventional sintered ones. Microstructure of all the conventional and microwave sintered samples was observed using high resolution scanning electron microscope. Although epsilon' and tauf of the conventional and microwave sintered samples are found to be comparable, the quality factor (the vital characteristic of dielectric resonators) of microwave sintered samples are observed to be much lower than those obtained by conventional sintering. The difference in these values is discussed with respect to the grain size.

  14. Diffusion-facilitated direct determination of intrinsic parameters for rapid photoinduced bimolecular electron-transfer reactions in nonpolar solvents.

    PubMed

    Scully, Andrew D; Ohtaka, Hiroyasu; Takezaki, Makoto; Tominaga, Toshihiro

    2015-03-26

    Bimolecular fluorescence-quenching reactions involving electron-transfer between electronically excited 5,10,15,20-tetraphenyl-21H,23H-porphine (TPP*) and 1,4-benzoquinone (BQ) or 1,4-naphthoquinone (NQ) were investigated using a set of alkane solvents that enabled the rapid reaction kinetics to be probed over a wide viscosity range, while minimizing changes in other relevant solvent parameters. Relative diffusion coefficients and reaction distances were recovered directly from analysis of fluorescence decay curves measured on a nanosecond time scale. The electron transfer from TPP* to BQ requires reactant contact, consistent with tightly associated exciplex formation in these nonpolar solvents. In contrast, electron transfer from TPP* to NQ displays a clear distance dependence, indicative of reaction via a much looser noncontact exciplex. This difference is attributed to the greater steric hindrance associated with contact between the TPP*/NQ pair. The diffusion coefficients recovered from fluorescence decay curve analysis are markedly smaller than the corresponding measured bulk relative diffusion coefficients. Classical hydrodynamics theory was found to provide a satisfactory resolution of this apparent discrepancy. The calculated hydrodynamic radii of TPP and NQ correlate very well with the van der Waals values. The hydrodynamic radius obtained for BQ is a factor of 6 times smaller than the van der Waals value, indicative of a possible tight cofacial geometry in the (TPP(+)/BQ(-))* exciplex. The present work demonstrates the utility of a straightforward methodology, based on widely available instrumentation and data analysis, that is broadly applicable for direct determination of kinetic parameter values for a wide variety of rapid bimolecular fluorescence quenching reactions in fluid solution.

  15. Sintered composite medium and filter

    DOEpatents

    Bergman, Werner

    1987-01-01

    A particulate filter medium is formed of a sintered composite of 0.5 micron diameter quartz fibers and 2 micron diameter stainless steel fibers. A preferred composition is about 40 vol. % quartz and about 60 vol. % stainless steel fibers. The media is sintered at about 1100.degree. C. to bond the stainless steel fibers into a cage network which holds the quartz fibers. High filter efficiency and low flow resistance are provided by the smaller quartz fibers. High strength is provided by the stainless steel fibers. The resulting media has a high efficiency and low pressure drop similar to the standard HEPA media, with tensile strength at least four times greater, and a maximum operating temperature of about 550.degree. C. The invention also includes methods to form the composite media and a HEPA filter utilizing the composite media. The filter media can be used to filter particles in both liquids and gases.

  16. Direct reforming of biogas on Ni-based SOFC anodes: Modelling of heterogeneous reactions and validation with experiments

    NASA Astrophysics Data System (ADS)

    Santarelli, Massimo; Quesito, Francesco; Novaresio, Valerio; Guerra, Cosimo; Lanzini, Andrea; Beretta, Davide

    2013-11-01

    This work focuses on the heterogeneous reactions taking place in a tubular anode-supported solid oxide fuel cell (SOFC) when the designated fuel is biogas from anaerobic digestion directly feeding the fuel cell. Operational maps of the fuel cell running on direct reforming of biogas were first obtained. Hence a mathematical model incorporating the kinetics of reforming reactions on Ni catalyst was used to predict the gas composition profile along the fuel channel. The model was validated against experimental data based on polarization curves. Also, the anode off-gas composition was collected and analyzed through a gas chromatograph. Finally, the model has been used to predict and analyze the gas composition change along the anode channel to evaluate effectiveness of the direct steam reforming when varying cell temperature, inlet fuel composition and the type of reforming process. The simulations results confirmed that thermodynamic-equilibrium conditions are not fully achieved inside the anode channel. It also outlines that a direct biogas utilization in an anode-supported SOFC is able to provide good performance and to ensure a good conversion of the methane even though when the cell temperature is far from the nominal value.

  17. Non-Sintered Nickel Electrode

    DOEpatents

    Bernard, Patrick; Dennig, Corinne; Cocciantelli, Jean-Michel; Alcorta, Jose; Coco, Isabelle

    2002-01-01

    A non-sintered nickel electrode contains a conductive support and a paste comprising an electrochemically active material containing nickel hydroxide and a binder which is a mixture of an elastomer and a crystalline polymer. The proportion of the elastomer is in the range 25% to 60% by weight of the binder and the proportion of the crystalline polymer is in the range 40% to 75% by weight of the binder.

  18. Ultra-fast and energy-efficient sintering of ceramics by electric current concentration

    PubMed Central

    Zapata-Solvas, E.; Gómez-García, D.; Domínguez-Rodríguez, A.; Todd, R. I.

    2015-01-01

    Electric current activated/assisted sintering (ECAS) techniques, such as electrical discharge sintering (EDS) or resistive sintering (RS), have been intensively investigated for longer than 50 years. In this work, a novel system including an electrically insulated graphite die for Spark Plasma Sintering (SPS) is described, which allows the sintering of any refractory ceramic material in less than 1 minute starting from room temperature with heating rates higher than 2000°C/min and an energy consumption up to 100 times lower than with SPS. The system alternates or combines direct resistive sintering (DRS) and indirect resistive sintering (IRS). Electrical insulation of the die has been achieved through the insertion of a film made of alumina fibers between the graphite die and the graphite punches, which are protected from the alumina fiber film by a graphite foil. This system localized the electric current directly through the sample (conductive materials) as in DRS and EDS, or through the thin graphite foil (non-conductive materials) as in IRS, and is the first system capable of being used under EDS or RS conditions independently combining current concentration/localization phenomena. PMID:25686537

  19. Directing the Lithium–Sulfur Reaction Pathway via Sparingly Solvating Electrolytes for High Energy Density Batteries

    PubMed Central

    2017-01-01

    The lithium–sulfur battery has long been seen as a potential next generation battery chemistry for electric vehicles owing to the high theoretical specific energy and low cost of sulfur. However, even state-of-the-art lithium–sulfur batteries suffer from short lifetimes due to the migration of highly soluble polysulfide intermediates and exhibit less than desired energy density due to the required excess electrolyte. The use of sparingly solvating electrolytes in lithium–sulfur batteries is a promising approach to decouple electrolyte quantity from reaction mechanism, thus creating a pathway toward high energy density that deviates from the current catholyte approach. Herein, we demonstrate that sparingly solvating electrolytes based on compact, polar molecules with a 2:1 ratio of a functional group to lithium salt can fundamentally redirect the lithium–sulfur reaction pathway by inhibiting the traditional mechanism that is based on fully solvated intermediates. In contrast to the standard catholyte sulfur electrochemistry, sparingly solvating electrolytes promote intermediate- and short-chain polysulfide formation during the first third of discharge, before disproportionation results in crystalline lithium sulfide and a restricted fraction of soluble polysulfides which are further reduced during the remaining discharge. Moreover, operation at intermediate temperatures ca. 50 °C allows for minimal overpotentials and high utilization of sulfur at practical rates. This discovery opens the door to a new wave of scientific inquiry based on modifying the electrolyte local structure to tune and control the reaction pathway of many precipitation–dissolution chemistries, lithium–sulfur and beyond. PMID:28691072

  20. Directing the Lithium-Sulfur Reaction Pathway via Sparingly Solvating Electrolytes for High Energy Density Batteries.

    PubMed

    Lee, Chang-Wook; Pang, Quan; Ha, Seungbum; Cheng, Lei; Han, Sang-Don; Zavadil, Kevin R; Gallagher, Kevin G; Nazar, Linda F; Balasubramanian, Mahalingam

    2017-06-28

    The lithium-sulfur battery has long been seen as a potential next generation battery chemistry for electric vehicles owing to the high theoretical specific energy and low cost of sulfur. However, even state-of-the-art lithium-sulfur batteries suffer from short lifetimes due to the migration of highly soluble polysulfide intermediates and exhibit less than desired energy density due to the required excess electrolyte. The use of sparingly solvating electrolytes in lithium-sulfur batteries is a promising approach to decouple electrolyte quantity from reaction mechanism, thus creating a pathway toward high energy density that deviates from the current catholyte approach. Herein, we demonstrate that sparingly solvating electrolytes based on compact, polar molecules with a 2:1 ratio of a functional group to lithium salt can fundamentally redirect the lithium-sulfur reaction pathway by inhibiting the traditional mechanism that is based on fully solvated intermediates. In contrast to the standard catholyte sulfur electrochemistry, sparingly solvating electrolytes promote intermediate- and short-chain polysulfide formation during the first third of discharge, before disproportionation results in crystalline lithium sulfide and a restricted fraction of soluble polysulfides which are further reduced during the remaining discharge. Moreover, operation at intermediate temperatures ca. 50 °C allows for minimal overpotentials and high utilization of sulfur at practical rates. This discovery opens the door to a new wave of scientific inquiry based on modifying the electrolyte local structure to tune and control the reaction pathway of many precipitation-dissolution chemistries, lithium-sulfur and beyond.

  1. Directing the lithium–sulfur reaction pathway via sparingly solvating electrolytes for high energy density batteries

    DOE PAGES

    Lee, Chang -Wook; Pang, Quan; Ha, Seungbum; ...

    2017-05-25

    The lithium–sulfur battery has long been seen as a potential next generation battery chemistry for electric vehicles owing to the high theoretical specific energy and low cost of sulfur. However, even state-of-the-art lithium–sulfur batteries suffer from short lifetimes due to the migration of highly soluble polysulfide intermediates and exhibit less than desired energy density due to the required excess electrolyte. The use of sparingly solvating electrolytes in lithium–sulfur batteries is a promising approach to decouple electrolyte quantity from reaction mechanism, thus creating a pathway toward high energy density that deviates from the current catholyte approach. Herein, we demonstrate that sparinglymore » solvating electrolytes based on compact, polar molecules with a 2:1 ratio of a functional group to lithium salt can fundamentally redirect the lithium–sulfur reaction pathway by inhibiting the traditional mechanism that is based on fully solvated intermediates. In contrast to the standard catholyte sulfur electrochemistry, sparingly solvating electrolytes promote intermediate- and short-chain polysulfide formation during the first third of discharge, before disproportionation results in crystalline lithium sulfide and a restricted fraction of soluble polysulfides which are further reduced during the remaining discharge. Moreover, operation at intermediate temperatures ca. 50 °C allows for minimal overpotentials and high utilization of sulfur at practical rates. Finally, this discovery opens the door to a new wave of scientific inquiry based on modifying the electrolyte local structure to tune and control the reaction pathway of many precipitation–dissolution chemistries, lithium–sulfur and beyond.« less

  2. Low Temperature Sintering of PZT

    NASA Astrophysics Data System (ADS)

    Medesi, A.; Greiner, T.; Benkler, M.; Megnin, C.; Hanemann, T.

    2014-11-01

    This paper describes the fabrication and characterization of lead zirconate titanate (PZT) films fired in a liquid-phase sintering process at 900 °C in air. In detail the manufacturing of piezoelectric multilayers with internal pure silver (Tm = 961 °C) electrodes are reported. The feasibility of ten sintering aids in two different volume fractions was investigated for a commercial hard PZT powder (PIC 181, PI Ceramics) with respect to density, microstructure, mechanical behaviour, and piezoelectric properties. Li2O, Li2CO3, PbO, MnO2, V2O5, CuO, Bi2O3, the eutectic mixtures Cu2O·PbO and PbO·WO3 and the ternary system Li2CO3·Bi2O3·CuO (LBCu) have been tested as liquid phase sintering aids. The combination of PZT with LBCu showed the best results. With 5 vol.% LBCu an average relative density of 97% and a characteristic breaking strength of 77 MPa was achieved. Composition of PZT with 2 vol.% LBCu exhibits the highest averaged piezoelectrical charge constant (d33) of 181 pC/N.

  3. Psychophysiological reactions in dental phobic patients with direct vs. indirect fear acquisition.

    PubMed

    Lundgren, Jesper; Berggren, Ulf; Carlsson, Sven G

    2004-03-01

    Dental phobic patients with reported traumatic experiences at onset of dental anxiety were compared to subjects with an indirect fear acquisition in their psychophysiological responses to video scenes showing dental procedures. It has been suggested that individuals with conditioned fear would respond with higher levels of physiological arousal in response to threat compared to subjects with indirect fear acquisition. Although the overall pattern indicates support for this hypothesis, subjects grouped on the basis of their reported fear-etiology did not statistically differ in recorded muscle tension, heart rate or skin conductance reactions to fear-provoking conditions.

  4. Direct conversion of cellulose and hemicellulose to fermentable sugars by a microbially-driven Fenton reaction.

    PubMed

    Sekar, Ramanan; Shin, Hyun Dong; DiChristina, Thomas J

    2016-10-01

    The aim of this work was to develop a microbially-driven Fenton reaction that fragments cellulose and hemicellulose, degrades cellodextrins and xylodextrins, and produces short-chain oligosaccharides and monomeric sugars in a single bioreactor. The lignocellulose degradation system operates at neutral pH and does not require addition of conventional lignocellulose-degrading enzymes, thus avoiding problems associated with enzyme accessibility and specificity. The ability to produce useful bioproducts was demonstrated by production of the bioplastic polyhydroxybutyrate with the xylan degradation products as starting substrate.

  5. Yield ratios and directed flows of light fragments from reactions induced by neutron-rich nuclei at intermediate energy

    NASA Astrophysics Data System (ADS)

    Yan, Ting-Zhi; Li, Long-Long; Wang, Rui-Feng; Yan, Ting-Feng

    2017-04-01

    The yield ratios of neutron/proton and 3H/3He and the directed flow per nucleon for these projectile-like fragments at large impact parameters are studied for 50Ca + 40Ca and 50Cr + 40Ca for comparison at 50 MeV/u using the isospin-dependent quantum molecular dynamics (IQMD) model. It is found that the yield ratios and the directed flows per nucleon are different for reactions induced by the neutron-rich nucleus 50Ca and the stable isobaric nucleus 50Cr, and depend on the hardness of the EOS. The ratios of neutron/proton and 3H/3He and the difference of directed flow per nucleon of neutron-proton are suggested to be possible observables to investigate the isospin effects. Supported by National Natural Science Foundation of China (11405025)

  6. Nuclear Ordered Phases of Solid 3He in Silver Sinters

    NASA Astrophysics Data System (ADS)

    Schuberth, Erwin A.; Kath, Matthias; Bago, Simone

    2006-09-01

    To determine the exact spin structure of the nuclear magnetic ordered phases of solid 3He, the U2D2 low field and the high field phases above 0.4 T, a European Research and Training Network for neutron scattering from the ordered solid was established which consisted of a collaboration with the Hahn Meitner Institute, Berlin, and other European and US groups. For this experiment it is crucial to grow a single crystal within the sinter needed for cooling the solid to temperatures of the order of 500 μK and to keep it cold long enough to measure a magnetic neutron diffraction. The sinter is also necessary to absorb the major part (> 90%) of the heat generated by the neutron capture and decay reaction of the 3He nucleus. In this work we studied the growth of crystals in Ag sinters of different pore sizes and with different growth speeds to find an optimal way to obtain single crystalline samples, or at least samples with only a few grains. We used SQUID magnetometry and NMR to measure the magnetization in the ordered phases. They were indicated by the known drop of the intensity, both in the NMR signal and in the dc magnetization, for the U2D2 phase, and by an increase of about 30% for the high field phase. The best results for cooling were obtained with sinters made from 700 Å "Japanese powder" with a packing fraction of 50% which were annealed at 130 °C after sintering and then had a calculated particle size of about 4200 Å. In the dc magnetization we found a paramagnetic surface contribution from a few monolayers of 3He down to 500 μK in addition to the bulk magnetization.

  7. Statistical Hauser-Feshbach theory with width-fluctuation correction including direct reaction channels for neutron-induced reactions at low energies

    NASA Astrophysics Data System (ADS)

    Kawano, T.; Capote, R.; Hilaire, S.; Chau Huu-Tai, P.

    2016-07-01

    A model to calculate particle-induced reaction cross sections with statistical Hauser-Feshbach theory including direct reactions is given. The energy average of the scattering matrix from the coupled-channels optical model is diagonalized by the transformation proposed by Engelbrecht and Weidenmüller [C. A. Engelbrecht and H. A. Weidenmüller, Phys. Rev. C 8, 859 (1973), 10.1103/PhysRevC.8.859]. The ensemble average of S -matrix elements in the diagonalized channel space is approximated by a model of Moldauer [P. A. Moldauer, Phys. Rev. C 12, 744 (1975), 10.1103/PhysRevC.12.744] using the newly parametrized channel degree-of-freedom νa to better describe the Gaussian orthogonal ensemble (GOE) reference calculations. The Moldauer approximation is confirmed by a Monte Carlo study using a randomly generated S matrix, as well as the GOE threefold integration formula. The method proposed is applied to the 238U(n ,n' ) cross-section calculation in the fast-energy range, showing an enhancement in the inelastic scattering cross sections.

  8. A Si/SiGe quantum well based biosensor for direct analysis of exothermic biochemical reaction

    NASA Astrophysics Data System (ADS)

    Zhang, Lei; Dong, Tao

    2013-04-01

    A rapid and reliable detection system is needed in the area of label-free calorimetric measurement for monitoring biochemical reactions. In this paper, a thermal biosensor employing a Si/SiGe quantum well is proposed where the infrared radiation energy is carefully considered to increase the sensor's sensitivity. It applies a suspended functional film with a trench across the multilayers. A polydimethylsiloxane cover for the microfluidic channel is bonded with the sensor for the injection and removal of a small volume of solution (down to 500 nL). The resistance change of Si/SiGe quantum well material is read out through the wire bonding connection to the conductive pads of the sensor. A linear detection range from 0.5 to 150 mM and a relative standard deviation less than 1% are demonstrated in the enzymatic reaction test with urea solution. Characterizations on the quantum well film verifies a high temperature coefficient of resistance value and fine crystal lattice, which promises a notable sensitivity. The application of the wafer level transfer bonding process makes the sensor fabrication convenient and cost-effective.

  9. Direct calculation of minimal cut sets involving a specific reaction knock-out.

    PubMed

    Tobalina, Luis; Pey, Jon; Planes, Francisco J

    2016-07-01

    The concept of Minimal Cut Sets (MCSs) is used in metabolic network modeling to describe minimal groups of reactions or genes whose simultaneous deletion eliminates the capability of the network to perform a specific task. Previous work showed that MCSs where closely related to Elementary Flux Modes (EFMs) in a particular dual problem, opening up the possibility to use the tools developed for computing EFMs to compute MCSs. Until recently, however, there existed no method to compute an EFM with some specific characteristic, meaning that, in the case of MCSs, the only strategy to obtain them was to enumerate them using, for example, the standard K-shortest EFMs algorithm. In this work, we adapt the recently developed theory to compute EFMs satisfying several constraints to the calculation of MCSs involving a specific reaction knock-out. Importantly, we emphasize that not all the EFMs in the dual problem correspond to real MCSs, and propose a new formulation capable of correctly identifying the MCS wanted. Furthermore, this formulation brings interesting insights about the relationship between the primal and the dual problem of the MCS computation. A Matlab-Cplex implementation of the proposed algorithm is available as a supplementary material fplanes@ceit.es Supplementary data are available at Bioinformatics online. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

  10. Direct assembly of multiply oxygenated carbon chains by decarbonylative radical-radical coupling reactions.

    PubMed

    Masuda, Kengo; Nagatomo, Masanori; Inoue, Masayuki

    2017-03-01

    Pentoses and hexoses contain more than three oxygen-bearing stereocentres and are ideal starting materials for the synthesis of multiply oxygenated natural products such as sagittamide D, maitotoxin and hikizimycin. Here we demonstrate new radical-radical homocoupling reactions of sugar derivatives with minimal perturbation of their chiral centres. The radical exchange procedure using Et3B/O2 converted sugar-derived α-alkoxyacyl tellurides into α-alkoxy radicals via decarbonylation and rapidly dimerized the monomeric radicals. The robustness of this process was demonstrated by a single-step preparation of 12 stereochemically diverse dimers with 6-10 secondary hydroxy groups, including the C5-C10 stereohexad of sagittamide D and the enantiomer of the C51-C60 stereodecad of maitotoxin. Furthermore, the optimally convergent radical-radical cross-coupling reaction achieved a one-step assembly of the protected C1-C11 oxygenated carbon chain of the anthelmintic hikizimycin. These exceptionally efficient homo- and heterocoupling methods together provide a powerful strategy for the expedited total synthesis of contiguously hydroxylated natural products.

  11. Direct assembly of multiply oxygenated carbon chains by decarbonylative radical-radical coupling reactions

    NASA Astrophysics Data System (ADS)

    Masuda, Kengo; Nagatomo, Masanori; Inoue, Masayuki

    2016-10-01

    Pentoses and hexoses contain more than three oxygen-bearing stereocentres and are ideal starting materials for the synthesis of multiply oxygenated natural products such as sagittamide D, maitotoxin and hikizimycin. Here we demonstrate new radical-radical homocoupling reactions of sugar derivatives with minimal perturbation of their chiral centres. The radical exchange procedure using Et3B/O2 converted sugar-derived α-alkoxyacyl tellurides into α-alkoxy radicals via decarbonylation and rapidly dimerized the monomeric radicals. The robustness of this process was demonstrated by a single-step preparation of 12 stereochemically diverse dimers with 6-10 secondary hydroxy groups, including the C5-C10 stereohexad of sagittamide D and the enantiomer of the C51-C60 stereodecad of maitotoxin. Furthermore, the optimally convergent radical-radical cross-coupling reaction achieved a one-step assembly of the protected C1-C11 oxygenated carbon chain of the anthelmintic hikizimycin. These exceptionally efficient homo- and heterocoupling methods together provide a powerful strategy for the expedited total synthesis of contiguously hydroxylated natural products.

  12. Direct kinetics study of the reaction of peroxyacetyl radical with NO between 218 and 370 K

    SciTech Connect

    Moise, T.; Denzer, W.; Rudich, Y.

    1999-08-26

    The rate coefficient of the CH{sub 3}C(O)O{sub 2} + NO gas-phase reaction was measured over the temperature range of 218--370 K and total pressure of 2--5 Torr, using chemical ionization mass spectrometry detection of the CH{sub 3}C(O)O{sub 2} radical. The temperature-dependent expression for the rate coefficient was determined to be {kappa}(T) = (6.0 {+-} 1.1) x 10{sup {minus}12} exp{l{underscore}brace}(320 {+-} 40)/T{r{underscore}brace} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}, and a 298 K rate constant {kappa}{sub 298} = (1.8 {+-} 0.3) x 10{sup {minus}11} cm{sup 3} molecule{sup {minus}1} was found. These results quell some of the ambiguity presented by previous studies of this reaction and validate the recommended value to be used in tropospheric chemistry models.

  13. Direct observation of periodic swelling and collapse of polymer chain induced by the Belousov-Zhabotinsky reaction.

    PubMed

    Hara, Yusuke; Mayama, Hiroyuki; Yamaguchi, Yoshinori; Takenaka, Yoshiko; Fukuda, Ryushi

    2013-11-21

    By utilizing a quartz crystal microbalance with dissipation (QCM-D), we directly observed the self-oscillating behavior of a polymer chain induced by the Belousov-Zhabotinsky (BZ) reaction. We succeeded in measuring self-oscillations of the resonance frequency (Δf) and dissipation (ΔD), which originate in the self-oscillating behavior of the polymer chain on a gold surface induced by the BZ reaction. We synthesized a self-oscillating polymer chain with Ru as the catalyst of the BZ reaction and a chemical adsorption site, so as to directly observe its periodic swelling and collapse on the gold surface. Distinct self-oscillation of ΔD synchronized with the self-oscillation Δf was observed. The period of the Δf self-oscillation was about 400 s, and the induction time was about 6.5 h. In QCM-D measurements, we found that the peaks of Δf and ΔD oscillations did not coincide in time because the state of the Gaussian chain did not coincide with the maximum value of Δf. Moreover, examination of the relationship between Δf and ΔD revealed that their oscillatory waveforms were identical in frequency but differed in phase and amplitude.

  14. Spike synchronization and firing rate in a population of motor cortical neurons in relation to movement direction and reaction time.

    PubMed

    Grammont, F; Riehle, A

    2003-05-01

    We studied the dynamics of precise spike synchronization and rate modulation in a population of neurons recorded in monkey motor cortex during performance of a delayed multidirectional pointing task and determined their relation to behavior. We showed that at the population level neurons coherently synchronized their activity at various moments during the trial in relation to relevant task events. The comparison of the time course of the modulation of synchronous activity with that of the firing rate of the same neurons revealed a considerable difference. Indeed, when synchronous activity was highest, at the end of the preparatory period, firing rate was low, and, conversely, when the firing rate was highest, at movement onset, synchronous activity was almost absent. There was a clear tendency for synchrony to precede firing rate, suggesting that the coherent activation of cell assemblies may trigger the increase in firing rate in large groups of neurons, although it appeared that there was no simple parallel shifting in time of these two activity measures. Interestingly, there was a systematic relationship between the amount of significant synchronous activity within the population of neurons and movement direction at the end of the preparatory period. Furthermore, about 400 ms later, at movement onset, the mean firing rate of the same population was also significantly tuned to movement direction, having roughly the same preferred direction as synchronous activity. Finally, reaction time measurements revealed a directional preference of the monkey with, once again, the same preferred direction as synchronous activity and firing rate. These results lead us to speculate that synchronous activity and firing rate are cooperative neuronal processes and that the directional matching of our three measures--firing rate, synchronicity, and reaction times--might be an effect of behaviorally induced network cooperativity acquired during learning.

  15. Rapid sintering of silicon nitride foams decorated with one-dimensional nanostructures by intense thermal radiation

    NASA Astrophysics Data System (ADS)

    Li, Duan; Guzi de Moraes, Elisângela; Guo, Peng; Zou, Ji; Zhang, Junzhan; Colombo, Paolo; Shen, Zhijian

    2014-08-01

    Silicon nitride foams were prepared by direct foaming and subsequent rapid sintering at 1600 °C. The intense thermal radiation generated under the pressureless spark plasma sintering condition facilitated necking of Si3N4 grains. The prepared foams possessed a porosity of ˜80 vol% and a compressive strength of ˜10 MPa, which required only ˜30 min for the entire sintering processes. Rapid growth of one-dimensional SiC nanowires from the cell walls was also observed. Thermodynamic calculations indicated that the vapor-liquid-solid model is applicable to the formation of SiC nanowires under vacuum.

  16. Rapid sintering of silicon nitride foams decorated with one-dimensional nanostructures by intense thermal radiation.

    PubMed

    Li, Duan; Guzi de Moraes, Elisângela; Guo, Peng; Zou, Ji; Zhang, Junzhan; Colombo, Paolo; Shen, Zhijian

    2014-08-01

    Silicon nitride foams were prepared by direct foaming and subsequent rapid sintering at 1600 °C. The intense thermal radiation generated under the pressureless spark plasma sintering condition facilitated necking of Si3N4 grains. The prepared foams possessed a porosity of ∼80 vol% and a compressive strength of ∼10 MPa, which required only ∼30 min for the entire sintering processes. Rapid growth of one-dimensional SiC nanowires from the cell walls was also observed. Thermodynamic calculations indicated that the vapor-liquid-solid model is applicable to the formation of SiC nanowires under vacuum.

  17. The influence of sintering on the dispersion of carbon nanotubes in ceramic matrix composites

    NASA Astrophysics Data System (ADS)

    Tapasztó, Orsolya; Lemmel, Hartmut; Markó, Márton; Balázsi, Katalin; Balázsi, Csaba; Tapasztó, Levente

    2014-10-01

    Optimizing the dispersion of carbon nanostructures in ceramic matrix composites is a fundamental technological challenge. So far most efforts have been focused on improving the dispersion of nanostructures during the powder phase processing, due to the limited information and control on their possible redistribution during the sintering. Here, we address this issue by comparing multi-walled carbon nanotubes reinforced Si3N4 composites prepared from the same starting powder dispersion but sintered using two different techniques. We employ ultra-small angle neutron scattering measurements to gain reliable information on the dispersion of nanostructures allowing a direct comparison of their redistribution during the sintering.

  18. Activity-Directed Synthesis with Intermolecular Reactions: Development of a Fragment into a Range of Androgen Receptor Agonists.

    PubMed

    Karageorgis, George; Dow, Mark; Aimon, Anthony; Warriner, Stuart; Nelson, Adam

    2015-11-09

    Activity-directed synthesis (ADS), a novel discovery approach in which bioactive molecules emerge in parallel with associated syntheses, was exploited to develop a weakly binding fragment into novel androgen receptor agonists. Harnessing promiscuous intermolecular reactions of carbenoid compounds enabled highly efficient exploration of chemical space. Four substrates were prepared, yet exploited in 326 reactions to explore diverse chemical space; guided by bioactivity alone, the products of just nine of the reactions were purified to reveal diverse novel agonists with up to 125-fold improved activity. Remarkably, one agonist stemmed from a novel enantioselective transformation; this is the first time that an asymmetric reaction has been discovered solely on the basis of the biological activity of the product. It was shown that ADS is a significant addition to the lead generation toolkit, enabling the efficient and rapid discovery of novel, yet synthetically accessible, bioactive chemotypes. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

  19. Directed assembly of defined oligomeric photosynthetic reaction centres through adaptation with programmable extra-membrane coiled-coil interfaces.

    PubMed

    Swainsbury, David J K; Harniman, Robert L; Di Bartolo, Natalie D; Liu, Juntai; Harper, William F M; Corrie, Alexander S; Jones, Michael R

    2016-12-01

    A challenge associated with the utilisation of bioenergetic proteins in new, synthetic energy transducing systems is achieving efficient and predictable self-assembly of individual components, both natural and man-made, into a functioning macromolecular system. Despite progress with water-soluble proteins, the challenge of programming self-assembly of integral membrane proteins into non-native macromolecular architectures remains largely unexplored. In this work it is shown that the assembly of dimers, trimers or tetramers of the naturally monomeric purple bacterial reaction centre can be directed by augmentation with an α-helical peptide that self-associates into extra-membrane coiled-coil bundle. Despite this induced oligomerisation the assembled reaction centres displayed normal spectroscopic properties, implying preserved structural and functional integrity. Mixing of two reaction centres modified with mutually complementary α-helical peptides enabled the assembly of heterodimers in vitro, pointing to a generic strategy for assembling hetero-oligomeric complexes from diverse modified or synthetic components. Addition of two coiled-coil peptides per reaction centre monomer was also tolerated despite the challenge presented to the pigment-protein assembly machinery of introducing multiple self-associating sequences. These findings point to a generalised approach where oligomers or longer range assemblies of multiple light harvesting and/or redox proteins can be constructed in a manner that can be genetically-encoded, enabling the construction of new, designed bioenergetic systems in vivo or in vitro.

  20. Exact model reduction with delays: closed-form distributions and extensions to fully bi-directional monomolecular reactions.

    PubMed

    Leier, Andre; Barrio, Manuel; Marquez-Lago, Tatiana T

    2014-06-06

    In order to systematically understand the qualitative and quantitative behaviour of chemical reaction networks, scientists must derive and analyse associated mathematical models. However, biochemical systems are often very large, with reactions occurring at multiple time scales, as evidenced by signalling pathways and gene expression kinetics. Owing to the associated computational costs, it is then many times impractical, if not impossible, to solve or simulate these systems with an appropriate level of detail. By consequence, there is a growing interest in developing techniques for the simplification or reduction of complex biochemical systems. Here, we extend our recently presented methodology on exact reduction of linear chains of reactions with delay distributions in two ways. First, we report that it is now possible to deal with fully bi-directional monomolecular systems, including degradations, synthesis and generalized bypass reactions. Second, we provide all derivations of associated delays in analytical, closed form. Both advances have a major impact on further reducing computational costs, while still retaining full accuracy. Thus, we expect our new methodology to respond to current simulation needs in pharmaceutical, chemical and biological research.

  1. Dual-level direct dynamics studies for the reactions of dimethyl ether with hydrogen atom and methyl radical.

    PubMed

    Wu, Jia-Yan; Liu, Jing-Yao; Li, Ze-Sheng; Huang, Xu-Ri; Sun, Chia-Chung

    2003-04-15

    The dual-level direct dynamics approach is employed to study the dynamics of the CH(3)OCH(3) + H (R1) and CH(3)OCH(3) + CH(3) (R2) reactions. Low-level calculations of the potential energy surface are carried out at the MP2/6-311+G(d,p) level of theory. High-level energetic information is obtained at the QCISD(T) level of theory with the 6-311+G(3df,3pd) basis set. The dynamics calculations are performed using variational transition state theory (VTST) with the interpolated single-point energies (ISPE) method, and small-curvature tunneling (SCT) is included. It is shown that the reaction of CH(3)OCH(3) with H (R1) may proceed much easier and with a lower barrier height than the reaction with CH(3) radical (R2). The calculated rate constants and activation energies are in good agreement with the experimental values. The calculated rate constants are fitted to k(R1) = 1.16 x 10(-19) T(3) exp(-1922/T) and k(R2) = 1.66 x 10(-28) T(5) exp(-3086/T) cm(3) mol(-1) s(-1) over a temperature range 207-2100 K. Furthermore, a small variational effect and large tunneling effect in the lower temperature range are found for the two reactions.

  2. Dual-level direct dynamics studies for the hydrogen abstraction reaction of 1,1-difluoroethane with O( 3P)

    NASA Astrophysics Data System (ADS)

    Liu, Jing-yao; Li, Ze-sheng; Dai, Zhen-wen; Zhang, Gang; Sun, Chia-chung

    2004-01-01

    We present dual-level direct dynamics calculations for the CH 3CHF 2 + O( 3P) hydrogen abstraction reaction in a wide temperature range, based on canonical variational transition-state theory including small curvature tunneling corrections. For this reaction, three distinct transition states, one for α-abstraction and two for β-abstraction, have been located. The potential energy surface information is obtained at the MP2(full)/6-311G(d,p) level of theory, and higher-level single-point calculations for the stationary points are preformed at several levels, namely QCISD(T)/6-311+G(3df,3pd), G2, and G3 using the MP2 geometries, as well as at the G3//MP4SDQ/6-311G(d,p) level. The energy profiles are further refined with the interpolated single-point energies method at the G3//MP2(full)/6-311G(d,p) level. The total rate constants match the experimental data reasonable well in the measured temperature range 1110-1340 K. It is shown that at low temperature α-abstraction may be the major reaction channel, while β-abstraction will have more contribution to the whole reaction rate as the temperature increases.

  3. Thermal conductivity evaluation of initial stage sintering phenomena

    NASA Astrophysics Data System (ADS)

    Schlaefer, Constance Elaine

    The onset of sinter bonding and concomitant handling strength is a critical period in the processing of powder metallurgy materials. Mechanical characterization of this evolution during predensification sintering is difficult, due to the fragile nature of the materials. Thermal properties such as thermal diffusivity and thermal conductivity also evolve during the onset of sinter bonding. This research investigates the potential for assessing mechanical strength through thermal diffusivity evaluation, using the non-contact technique of laser flash analysis. Thermal conductivity and transverse rupture strength were evaluated for a nickel powder system in three different formats: injection-molded, low-density die-compacted, and high-density die-compacted. Measurements focused on post-sintering strength and thermal conductivity evolution from 20 to 700°C for the first two formats. In situ strength was evaluated for the high-density die-compacted material. Thermal conductivity was demonstrated to be a linear function of neck diameter, versus a function of the neck area as anticipated. Strength evaluation confirmed previous research that strength is a function of the neck area. Based on both properties' dependence on neck size, an integrated relationship was constructed, allowing mechanical strength to be directly predicted from thermal conductivity measurement for the given system.

  4. Dye-sensitized solar cells based on nanocrystalline titania electrodes made at various sintering temperatures.

    PubMed

    Stathatos, Elias; Lianos, Panagiotis

    2007-02-01

    Dye-sensitized solar cells were made by using nanocrystalline titania deposited on Fluorine-doped SnO2 (FTO) electrodes. Nanocrystalline titania deposition was made by the sol-gel method using reverse micelles of bis(2-ethylhexyl) sulfosuccinate sodium salt (AOT) in cyclohexane as reaction medium. This surfactant could be easily removed from the deposited nanocomposite organic-inorganic film by simple rinsing with distilled water, without affecting titania adherence on FTO electrode. These nanocrystalline titania electrodes were used to make solar cells either without sintering or after sintering at various temperatures. Sintering extensively affected short circuit current but had small effect on device open-circuit voltage. Thus satisfactory photovoltaic response could be obtained even with devices made of non-sintered (room-temperature) titania.

  5. Gyrotron-Based Microwave Sintering of Ceramics

    NASA Astrophysics Data System (ADS)

    Fliflet, A. W.; Bruce, R. W.; Fischer Lewis, R. P., III; Bender, B. A.; Chow, G.-M.; Rayne, R. J.; Kurihara, L. K.; Schoen, P. E.

    1997-11-01

    The development of powerful gyrotrons has opened up the millimeter-wave regime (>= 28 GHz) for processing ceramic materials. A number of studies of microwave sintering of ceramics have indicated that sintering proceeds much faster in microwave furnaces than in conventional furnaces, however, specific conclusions have been limited by the wide range of materials investigated and measurement difficulties. To assess the potential of high frequency microwave sintering, and to investigate the possibility of a specific microwave mechanism, the Naval Research Laboratory has recently undertaken a systematic study focused on the sintering of fine and ultra-fine grained alumina and titania compacts. This paper presents 35 GHz microwave sintering data obtained using a gyrotron-powered furnace and compares our data with results from other microwave and conventional sintering studies.

  6. Investigation of chemical and electrochemical reactions mechanisms in a direct carbon fuel cell using olive wood charcoal as sustainable fuel

    NASA Astrophysics Data System (ADS)

    Elleuch, Amal; Halouani, Kamel; Li, Yongdan

    2015-05-01

    Direct carbon fuel cell (DCFC) is a high temperature fuel cell using solid carbon as fuel. The use of environmentally friendly carbon material constitutes a promising option for the DCFC future. In this context, this paper focuses on the use of biomass-derived charcoal renewable fuel. A practical investigation of Tunisian olive wood charcoal (OW-C) in planar DCFCs is conducted and good power density (105 mW cm-2) and higher current density (550 mA cm-2) are obtained at 700 °C. Analytical and predictive techniques are performed to explore the relationships between fuel properties and DCFC chemical and electrochemical mechanisms. High carbon content, carbon-oxygen groups and disordered structure, are the key parameters allowing the achieved good performance. Relatively complex chain reactions are predicted to explain the gas evolution within the anode. CO, H2 and CH4 participation in the anodic reaction is proved.

  7. Direct Measurement of the Effective Rate Constant for Primary Charge Separation in Isolated Photosystem II Reaction Centers

    SciTech Connect

    Greenfield, S. R.; Seibert, M.; Govindjee; Wasielewski, M. R.

    1997-03-27

    Transient absorption measurements of the pheophytin a anion band and Qx band bleach region using preferential excitation of P680 are performed on isolated photosystem II reaction centers to determine the effective rate constant for charge separtion. A novel analysis of the Qx band bleach region explicity takes the changing background into account in order to directly measure the rate of growth of the bleach. Both spectral regions reveal biphasic kinetics, with a ca. (8 ps)-1 rate constant for the faster component, and a ca. (50 ps)-1 rate constant for the slower component. We propose that the fster component corresponds to the effective rate constant for charge separation from within the equilibrated reaction center core and provides a lower limit for the intrinsic rate constant for charge separation. The slower component corresponds to charge separation that is limited by slow energy transfer from a long-wavelength accessory chlorophyll a.

  8. Estimation of kinetic parameters for enzyme-inhibition reaction models using direct time-dependent equations for reactant concentrations.

    PubMed

    Goličnik, Marko

    2012-03-01

    To facilitate the determination of a reaction type and its kinetics constants for reversible inhibitors of Michaelis-Menten-type enzymes using progress-curve analysis, I present here an explicit equation for direct curve fitting to full time-course data of inhibited enzyme-catalyzed reactions. This algebraic expression involves certain elementary functions where their values are readily available using any standard nonlinear regression program. Hence this allows easy analysis of experimentally observed kinetics without any data conversion prior to fitting. Its implementation gives correct parameter estimates that are in very good agreement with results obtained using both the numerically integrated Michaelis-Menten rate equation or its exact closed-form solution which is expressed in terms of the Lambert W function.

  9. Improvement of an acid phosphatase/DHAP-dependent aldolase cascade reaction by using directed evolution.

    PubMed

    van Herk, Teunie; Hartog, Aloysius F; Babich, Lara; Schoemaker, Hans E; Wever, Ron

    2009-09-04

    To enhance the phosphorylating activity of the bacterial nonspecific acid phosphatase from Salmonella enterica ser. typhimurium LT2 towards dihydroxyacetone (DHA), a mutant library was generated from the native enzyme. Three different variants that showed enhanced activity were identified after one round of epPCR. The single mutant V78L was the most active and showed an increase in the maximal DHAP concentration to 25 % higher than that of the wild-type enzyme at pH 6.0. This variant is 17 times more active than the wild-type acid phosphatase from Salmonella enterica ser. typhimurium LT2 in the acid phosphatase/aldolase cascade reaction at pH 6.0 and is also six times more active than the phosphatase from Shigella flexneri that we previously used.

  10. A novel mechanism for direct real-time polymerase chain reaction that does not require DNA isolation from prokaryotic cells.

    PubMed

    Soejima, Takashi; Xiao, Jin-Zhong; Abe, Fumiaki

    2016-06-23

    Typically, polymerase chain reaction (PCR) is performed after DNA isolation. Real-time PCR (qPCR), also known as direct qPCR in mammalian cells with weak membranes, is a common technique using crude samples subjected to preliminary boiling to elute DNA. However, applying this methodology to prokaryotic cells, which have solid cell walls, in contrast to mammalian cells which immediately burst in water, can result in poor detection. We successfully achieved PCR elongation with the addition of 1.3 cfu of Cronobacter muytjensii to a newly developed direct qPCR master mix without performing any crude DNA extraction (detection limit of 1.6 × 10(0) cfu/ml for the test sample compared with a detection limit of 1.6 × 10(3) cfu/ml primarily for crude (boiling) or classical DNA isolation). We revealed that the chromosomal DNA retained in prokaryotic cells can function as a PCR template, similarly to the mechanism in in situ PCR. Elucidating this reaction mechanism may contribute to the development of an innovative master mix for direct qPCR to detect genes in a single bacterium with solid cell walls and might lead to numerous novel findings in prokaryotic genomics research.

  11. A novel mechanism for direct real-time polymerase chain reaction that does not require DNA isolation from prokaryotic cells

    PubMed Central

    Soejima, Takashi; Xiao, Jin-zhong; Abe, Fumiaki

    2016-01-01

    Typically, polymerase chain reaction (PCR) is performed after DNA isolation. Real-time PCR (qPCR), also known as direct qPCR in mammalian cells with weak membranes, is a common technique using crude samples subjected to preliminary boiling to elute DNA. However, applying this methodology to prokaryotic cells, which have solid cell walls, in contrast to mammalian cells which immediately burst in water, can result in poor detection. We successfully achieved PCR elongation with the addition of 1.3 cfu of Cronobacter muytjensii to a newly developed direct qPCR master mix without performing any crude DNA extraction (detection limit of 1.6 × 100 cfu/ml for the test sample compared with a detection limit of 1.6 × 103 cfu/ml primarily for crude (boiling) or classical DNA isolation). We revealed that the chromosomal DNA retained in prokaryotic cells can function as a PCR template, similarly to the mechanism in in situ PCR. Elucidating this reaction mechanism may contribute to the development of an innovative master mix for direct qPCR to detect genes in a single bacterium with solid cell walls and might lead to numerous novel findings in prokaryotic genomics research. PMID:27334801

  12. [Decoloration and degradation of direct pink 12B by microwave-promoted heterogeneous Fenton-like reaction].

    PubMed

    Zheng, Huai-Li; Xie, Li-Guo; Hu, Peng; Jiao, Shi-Jun; Hu, Xue-Bin; Liu, Lan; Wu, You-Quan

    2010-06-01

    Microwave-promoted heterogeneous Fenton-like reaction, the combination of Fenton-like reagent with microwave, is an efficient method for waste water treatment. In the present paper, the degradation of direct pink 12B (a kind of organic dye) was studied using this method was studied. Through numerous experiments, the influences of various parameters including the initial pH value, dosage of Fe-Ni-Mn/AlO3, dosage of H2O2 and microwave were investigated intensively. The characteristic curve of direct pink12B, the concentration-absorbency curve of direct pink12B, the orthogonal optimization tests and comparative tests were given. In this paper, the mechanisms of this reaction were also been probed. It is concluded from the experiments that the microwave can accelerate the process of degradation effectively. Under optimal conditions, the overall color removal was more than 99.0% within 10 min. In the study, all the characterization was carried out using UV-Vis spectral-analysis.

  13. Feasibility of Traveling Wave Direct Energy Conversion of Fission Reaction Fragments

    NASA Technical Reports Server (NTRS)

    Tarditi, A. G.; George, J. A.; Miley, G. H.; Scott, J. H.

    2013-01-01

    Fission fragment direct energy conversion has been considered in the past for the purpose of increasing nuclear power plant efficiency and for advanced space propulsion. Since the fragments carry electric charge (typically in the order of 20 e) and have 100 MeV-range kinetic energy, techniques utilizing very high-voltage DC electrodes have been considered. This study is focused on a different approach: the kinetic energy of the charged fission fragments is converted into alternating current by means of a traveling wave coupling scheme (Traveling Wave Direct Energy Converter, TWDEC), thereby not requiring the utilization of high voltage technology. A preliminary feasibility analysis of the concept is introduced based on a conceptual level study and on a particle simulation model of the beam dynamics.

  14. Pulp tissue reactions to a dentin bonding agent as a direct capping agent.

    PubMed

    Sübay, Rüstem Kemal; Demirci, Mustafa

    2005-03-01

    The aim of this study was to investigate the response of human pulp tissue to a dentin bonding agent, Scotchbond Multi-Purpose Plus (SMPP), in exposed class V cavities. Sixteen human premolar teeth were mechanically exposed. Ten pulps were capped with SMPP and six teeth were capped with Dycal. The cavities were filled with a composite. After 40 days, the teeth were extracted and processed for histologic evaluation. Of the 10 teeth capped with SMPP, eight showed moderate chronic inflammation, one was severely inflamed, and one pulp had no to slight inflammation. None of the teeth capped with SMPP showed dentin bridge formation. Of the six teeth capped with Dycal, three exhibited incomplete dentin bridges associated with no to slight inflammation, and three showed no to slight inflammation, without formation of dentin bridges. Direct capping with Dycal with subsequent sealing with SMPP may show favorable results in pulp tissue. SMPP may cause inflammatory changes when applied directly to exposed pulp tissue.

  15. Nonenzymatic template-directed reactions on altritol oligomers, preorganized analogues of oligonucleotides

    NASA Technical Reports Server (NTRS)

    Kozlov, I. A.; Zielinski, M.; Allart, B.; Kerremans, L.; Van Aerschot, A.; Busson, R.; Herdewijn, P.; Orgel, L. E.; Bada, J. L. (Principal Investigator)

    2000-01-01

    Altritol nucleic acids (ANAs) are RNA analogues with a phosphorylated D-altritol backbone. The nucleobase is attached at the 2-(S)-position of the carbohydrate moiety. We report that ANA oligomers are superior to the corresponding DNA, RNA, and HNA (hexitol nucleic acid) in supporting efficient nonenzymatic template-directed synthesis of complementary RNAs from nucleoside-5'-phosphoro-2-methyl imidazolides. Activated ANA and HNA monomers do not oligomerize efficiently on DNA, RNA, HNA, or ANA templates.

  16. A Common Selection Rule for Organic Reactions in Terms of Signs of Direct and Indirect Interorbital Interactions

    NASA Astrophysics Data System (ADS)

    Gineityte, Viktorija

    2009-02-01

    The semilocalized approach to chemical reactivity suggested recently is overviewed with respect to both theory and applications. The principal attention is paid to formulation of a common selection rule for organic reactions and to demonstration of its validity to various heterolytic (i. e. nucleophilic and electrophilic) and pericyclic processes. The total energy of the whole reacting system (E) is represented in this approach in the form of power series with respect to all interfragmental interactions (fragments coincide with individual chemical bonds, phenyl rings, etc.). For any reaction, a certain decisive k-th-order energy correction E(k) may be revealed, the sign of which depends on the actual way of the process. The allowed and forbidden reactions are then defined as those described by negative (stabilizing) and positive (destabilizing) corrections E(k), respectively. The condition which ensures the negative sign of E(k) resolves itself into a universal requirement of coinciding signs of the principal direct and indirect interactions of basis orbitals localized on separate fragments (e. g. bond orbitals). This result forms the basis for the above-mentioned selection rule. Allowed (forbidden) ways of heterolytic reactions are exemplified by the back (frontal) attack of a nucleophile upon a substituted alkane in the SN2 process, the meta (ortho, para) attacks of electrophile upon the pyridine molecule, the addition of electrophile to the Cβ (Cα ) atom of a donor-containing derivative of ethene (D-CαH=Cβ H2), the trans (cis)-β -elimination processes of substituted alkanes, etc. Application of the same rule to pericyclic reactions is demonstrated to yield predictions coinciding with those of other approaches including the famous Woodward-Hoffmann rule.

  17. Sintering and microstructural development of metal oxide varistor ceramics

    SciTech Connect

    Makovec, D.; Kolar, D.; Trontelj, M. . Jozef Stefan Institute)

    1993-08-01

    Anomalous retardation of the sintering kinetics of ZnO with addition of Bi[sub 4]Ti[sub 3]O[sub 12] (BIT) and a low voltage varistor composition containing ZnO, BIT, Co[sub 3]O[sub 4] and Mn[sub 2]O[sub 3] in the temperature interval between 780 and 850 C was investigated. On the basis of transmission electron microscopic analysis of diffusion couples the retardation of sintering kinetics was ascribed to surface diffusion of Bi and Ti along ZnO grain surfaces. Liquid phase formation resulting from chemical reactions between the components triggers exaggerated grain growth. Nucleation and growth of anomalous grains is influenced by the presence of inversion boundaries in ZnO grains.

  18. The sintering behavior of ultrafine alumina particles

    SciTech Connect

    Bonevich, J.E.; Marks, L.D. )

    1992-06-01

    Ultrafine particles (UFPs) of aluminum oxide were prepared by an arc discharge, sintered in a custom-built ultrahigh vacuum (UHV) furnace system, and characterized in a high resolution electron microscope (HREM) operating under UHV conditions. The UFPs produced range in size from 20 to 50 nm and have highly faceted surfaces. The atomic structure of the UFPs corresponds to the cubic ({gamma}) and orthorhombic ({delta}) variants of the spinel structure. Sintering in these UFPs demonstrates three major issues. Surface faceting plays a major role in determining the final sintering geometry with sintering occurring predominantly on the closed-packed {l brace}111{r brace} facets. Surface diffusion is the predominant mechanism for sintering, as evidenced by the fact that many sintered particles have their initial adhesion structure locked-in' during sintering with no reorientation occurring. Furthermore, the necks formed during sintering have well-defined, atomically-sharp contact angles which suggests that the neck growth process is controlled by the faceted structures and may be modeled by a mechanism similar to crystal growth due to ledges, grain boundaries, and twins. The driving force for sintering can be considered as a chemical potential difference between facet surfaces and the neck region.

  19. Influence of Pressure in Flash Sintering Technique

    NASA Astrophysics Data System (ADS)

    Pcheliakov, D. A.; Yurlova, M. S.; Grigoryev, E. G.; Olevsky, E. A.

    An innovative pressure-assisted flash-sintering technique has been developed to investigate the effect of pressure applied on microstructure and the sintering behavior of titanium dioxide. There are numerous applications for titanium dioxide in ceramics including microeletronics, glass ceramics, refractive materials, structural ceramics and titanium-containing ceramic materials and chemical intermediates. The traditional sintering of titanium dioxide usually requires several hours at over 1200 °C. The conducted research indicates that titanium dioxide can be sintered to full density in only a few seconds at 800-1000 °C, when subjected to a DC electrical field at a certain temperature moment.

  20. On the sintering of silicon carbide

    NASA Technical Reports Server (NTRS)

    Gugel, E.

    1986-01-01

    This document deals with the sintering of silicon carbide using pressureless sintering. This technique makes it possible to sinter a primarily covalent material to usable densities up to over 98% thD without having to use a high amount of sinter additives as is the case with other non-oxide ceramic materials. The process takes place rapidly, and it is also possible to produce relatively thick-walled structural parts without major problems. This sheds more light on the true characteristics of silicon carbide in one structural part, since there is no second or nearly no second phase. Heat pressing has improved stability.

  1. Low temperature plasma sintering of silver nanoparticles

    NASA Astrophysics Data System (ADS)

    Ma, Siyuan; Bromberg, Vadim; Liu, Liang; Egitto, Frank D.; Chiarot, Paul R.; Singler, Timothy J.

    2014-02-01

    The fabrication of flexible electronics using the deposition of solution-processed nanomaterials generally requires low-temperature post-processing to optimize functionality. We studied sintering of silver nanoparticle (AgNP) films on glass substrates by applying argon (Ar) plasma to achieve improved electrical conductivity. This process meets the low temperature processing requirements for standard low-cost polymeric flexible substrates. The relationship between plasma parameters (such as power and sintering time) versus sintering results (such as electrical sheet resistance, sintered structure depth, materials composition variation, and film nanostructure) is reported for 23 and 77 nm diameter AgNPs. In addition, plasma processing typically induces a small surface thermal effect. We monitored the surface temperatures of the AgNP films in-situ during plasma sintering. By sintering control groups at these monitored surface temperatures using a vacuum oven, we confirmed that the resistivity due to plasma sintering is less than that produced by thermal sintering. Our data show that, the measured lowest resistivities for plasma sintered AgNP films are about only 5 and 12 times greater than the bulk Ag resistivity for 23 and 77 nm, respectively.

  2. Exothermic low temperature sintering of Cu nanoparticles

    SciTech Connect

    Mittal, Jagjiwan; Lin, Kwang-Lung

    2015-11-15

    Sintering of the Cu nanoparticle at low temperatures resulted in exothermic behavior after its initiation. The calorimetry study of the heating of a 20 nm copper nanoparticles agglomerate revealed the evolution of 41.17 J/g of heat between 170 °C and 270 °C. High resolution transmission electron microscopy (HRTEM) images indicated that the heat generation was accompanied by sintering. The surface energy of the 20 nm copper nanoparticles was estimated to be 1.23 × 10{sup 3} erg/cm{sup 2} based on the heat released during sintering. The in situ high resolution transmission electron microscope (HRTEM) investigation showed that vigorous sintering occurred between 217 and 234 °C, which took place through the dislocation sintering mechanism. - Highlights: • Calorimetry showed exothermic behavior during heating of Cu nanoparticles between 170 and 270 °C. • Heat released due to the sintering of Cu nanoparticles was demonstrated by HRTEM. • Surface energy of 20 nm copper nanoparticles was estimated to be 1.23 × 10{sup 3} erg/cm{sup 2} during sintering. • Growth in crystallite sizes during sintering is disclosed by X-ray diffraction. • In situ HRTEM heating study showed occurrence of sintering through dislocation mechanism.

  3. Permeability, drying, and sintering of pressure filtered ceramic nanopowders

    NASA Astrophysics Data System (ADS)

    Sweeney, Sean M.

    2002-01-01

    point of drying (when fracture is most likely during drying). Agreement between maximum safe drying stresses and measured sample strengths is found to be good (to within better than a factor of 2) for boehmite samples, but not very good (off by a factor of ˜7) for nanocrystalline 3Y-TZP samples. Sub-critical crack growth is indicated as the source of this deviation in nanocrystalline 3Y-TZP samples. Literature studies of the sintering of chloride-derived 3Y-TZP nanopowders have documented numerous sintering problems including inability to reach full density, desintering, cracking, and the formation of a dense shell with less dense interior. To explain the poor sintering behavior of samples of one nanocrystalline 3Y-TZP powder, the origin of such a dense shell microstructure is determined. Three possible reasons for a dense shell microstructure are examined and rejected: exothermic reactions with the sintering atmosphere, pre-existing density gradients in the green compact, and thermal gradients occurring during sintering. A combination of gas flow/diffusion, thermodynamic, and sintering calculations are used to show that the evolution of a structure-coarsening gas (hydrogen chloride) during sintering causes the formation of a dense shell microstructure, and explains the poor densification behavior of this system. Two solutions to the problem are compared: (1) a thermal treatment composed of an extended hold at 1000°C to allow HCl gas removal before the onset of closed porosity (at about 90-93% of theoretical density), and (2) a chemical treatment performed by washing pre-sintered (500°C/30 min) samples at room temperature using a concentrated ammonium hydroxide solution to remove chlorides. The thermal treatment is found to be superior for removing residual chlorine and allowing full density to be achieved during sintering.

  4. Towards organo-click reactions: development of pharmaceutical ingredients by using direct organocatalytic bio-mimetic reductions.

    PubMed

    Ramachary, Dhevalapally B; Reddy, G Babul

    2006-12-21

    Economic and environmentally friendly bio-mimetic one-pot three and four-component Knoevenagel-hydrogenation (K-H), five-component Knoevenagel-hydrogenation-alkylation (K-H-A) and six-component Knoevenagel-hydrogenation-alkylation-Huisgen cycloaddition (K-H-A-HC) reactions of aldehydes, CH-acids, o-phenylenediamine, alkyl halides and azides using proline, proline-metal carbonate and proline-metal carbonate-Cu(I)-catalysis, respectively have been developed. Many of K-H and K-H-A compounds have direct application in pharmaceutical chemistry.

  5. Phosphine-directed C-H borylation reactions: facile and selective access to ambiphilic phosphine boronate esters.

    PubMed

    Crawford, Kristina M; Ramseyer, Timothy R; Daley, Christopher J A; Clark, Timothy B

    2014-07-14

    Ambiphilic ligands have received considerable attention over the last two decades due to their unique reactivity as organocatalysts and ligands. The iridium-catalyzed C-H borylation of phosphines is described in which the phosphine is used as a directing group to provide selective formation of arylboronate esters with unique scaffolds of ambiphilic compounds. A variety of aryl and benzylic phosphines were subjected to the reaction conditions, selectively providing stable, isolable boronate esters upon protection of the phosphine as the borane complex. After purification, the phosphine-substituted boronate esters could be deprotected and isolated in pure form. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Direct measurements of unimolecular and bimolecular reaction kinetics of the Criegee intermediate (CH3)2COO

    DOE PAGES

    Chhantyal-Pun, Rabi; Welz, Oliver; Savee, John D.; ...

    2016-10-18

    Here, the Criegee intermediate acetone oxide, (CH3)2COO, is formed by laser photolysis of 2,2-diiodopropane in the presence of O2 and characterized by synchrotron photoionization mass spectrometry and by cavity ring-down ultraviolet absorption spectroscopy. The rate coefficient of the reaction of the Criegee intermediate with SO2 was measured using photoionization mass spectrometry and pseudo-first-order methods to be (7.3 ± 0.5) × 10–11 cm3 s–1 at 298 K and 4 Torr and (1.5 ± 0.5) × 10–10 cm3 s–1 at 298 K and 10 Torr (He buffer). These values are similar to directly measured rate coefficients of anti-CH3CHOO with SO2, and inmore » good agreement with recent UV absorption measurements. The measurement of this reaction at 293 K and slightly higher pressures (between 10 and 100 Torr) in N2 from cavity ring-down decay of the ultraviolet absorption of (CH3)2COO yielded even larger rate coefficients, in the range (1.84 ± 0.12) × 10–10 to (2.29 ± 0.08) × 10–10 cm3 s–1. Photoionization mass spectrometry measurements with deuterated acetone oxide at 4 Torr show an inverse deuterium kinetic isotope effect, kH/kD = (0.53 ± 0.06), for reactions with SO2, which may be consistent with recent suggestions that the formation of an association complex affects the rate coefficient. The reaction of (CD3)2COO with NO2 has a rate coefficient at 298 K and 4 Torr of (2.1 ± 0.5) × 10–12 cm3 s–1 (measured with photoionization mass spectrometry), again similar to rate for the reaction of anti-CH3CHOO with NO2. Cavity ring-down measurements of the acetone oxide removal without added reagents display a combination of first- and second-order decay kinetics, which can be deconvolved to derive values for both the self-reaction of (CH3)2COO and its unimolecular thermal decay. The inferred unimolecular decay rate coefficient at 293 K, (305 ± 70) s–1, is similar to determinations from ozonolysis. The present measurements confirm the large rate coefficient for

  7. Amine-catalyzed direct aldol reactions of hydroxy- and dihydroxyacetone: biomimetic synthesis of carbohydrates.

    PubMed

    Popik, Oskar; Pasternak-Suder, Monika; Leśniak, Katarzyna; Jawiczuk, Magdalena; Górecki, Marcin; Frelek, Jadwiga; Mlynarski, Jacek

    2014-06-20

    This article presents comprehensive studies on the application of primary, secondary, and tertiary amines as efficient organocatalysts for the de novo synthesis of ketoses and deoxyketoses. Mimicking the actions of aldolase enzymes, the synthesis of selected carbohydrates was accomplished in aqueous media by using proline- and serine-based organocatalysts. The presented methodology also provides direct access to unnatural L-carbohydrates from the (S)-glyceraldehyde precursor. Determination of the absolute configuration of all obtained sugars was feasible using a methodology consisting of concerted ECD and VCD spectroscopy.

  8. Direct measurements of OH and other product yields from the HO2 + CH3C(O)O2 reaction

    NASA Astrophysics Data System (ADS)

    Winiberg, F. A. F.; Dillon, T. J.; Orr, S. C.; Groß, C. B. M.; Bejan, I.; Brumby, C. A.; Evans, M. J.; Smith, S. C.; Heard, D. E.; Seakins, P. W.

    2015-10-01

    The reaction CH3C(O)O2 + HO2 → CH3C(O)OOH + O2 (Reaction R5a), CH3C(O)OH + O3 (Reaction R5b), CH3 + CO2 + OH + O2 (Reaction R5c) was studied in a series of experiments conducted at 1000 mbar and (293 ± 2) K in the HIRAC simulation chamber. For the first time, products, (CH3C(O)OOH, CH3C(O)OH, O3 and OH) from all three branching pathways of the reaction have been detected directly and simultaneously. Measurements of radical precursors (CH3OH, CH3CHO), HO2 and some secondary products HCHO and HCOOH further constrained the system. Fitting a comprehensive model to the experimental data, obtained over a range of conditions, determined the branching ratios α(R5a) = 0.37 ± 0.10, α(R5b) = 0.12 ± 0.04 and α(R5c) = 0.51 ± 0.12 (errors at 2σ level). Improved measurement/model agreement was achieved using k(R5) = (2.4 ± 0.4) × 10-11 cm3 molecule-1 s-1, which is within the large uncertainty of the current IUPAC and JPL recommended rate coefficients for the title reaction. The rate coefficient and branching ratios are in good agreement with a recent study performed by Groß et al. (2014b); taken together, these two studies show that the rate of OH regeneration through Reaction (R5) is more rapid than previously thought. GEOS-Chem has been used to assess the implications of the revised rate coefficients and branching ratios; the modelling shows an enhancement of up to 5 % in OH concentrations in tropical rainforest areas and increases of up to 10 % at altitudes of 6-8 km above the equator, compared to calculations based on the IUPAC recommended rate coefficient and yield. The enhanced rate of acetylperoxy consumption significantly reduces PAN in remote regions (up to 30 %) with commensurate reductions in background NOx.

  9. Direct measurements of OH and other product yields from the HO2 + CH3C(O)O2 reaction

    NASA Astrophysics Data System (ADS)

    Winiberg, Frank A. F.; Dillon, Terry J.; Orr, Stephanie C.; Groß, Christoph B. M.; Bejan, Iustinian; Brumby, Charlotte A.; Evans, Matthew J.; Smith, Shona C.; Heard, Dwayne E.; Seakins, Paul W.

    2016-03-01

    The reaction CH3C(O)O2 + HO2 → CH3C(O)OOH + O2 (Reaction R5a), CH3C(O)OH + O3 (Reaction R5b), CH3 + CO2 + OH + O2 (Reaction R5c) was studied in a series of experiments conducted at 1000 mbar and (293 ± 2) K in the HIRAC simulation chamber. For the first time, products, (CH3C(O)OOH, CH3C(O)OH, O3 and OH) from all three branching pathways of the reaction have been detected directly and simultaneously. Measurements of radical precursors (CH3OH, CH3CHO), HO2 and some secondary products HCHO and HCOOH further constrained the system. Fitting a comprehensive model to the experimental data, obtained over a range of conditions, determined the branching ratios α(R5a) = 0.37 ± 0.10, α(R5b) = 0.12 ± 0.04 and α(R5c) = 0.51 ± 0.12 (errors at 2σ level). Improved measurement/model agreement was achieved using k(R5) = (2.4 ± 0.4) × 10-11 cm3 molecule-1 s-1, which is within the large uncertainty of the current IUPAC and JPL recommended rate coefficients for the title reaction. The rate coefficient and branching ratios are in good agreement with a recent study performed by Groß et al. (2014b); taken together, these two studies show that the rate of OH regeneration through Reaction (R5) is more rapid than previously thought. GEOS-Chem has been used to assess the implications of the revised rate coefficients and branching ratios; the modelling shows an enhancement of up to 5 % in OH concentrations in tropical rainforest areas and increases of up to 10 % at altitudes of 6-8 km above the equator, compared to calculations based on the IUPAC recommended rate coefficient and yield. The enhanced rate of acetylperoxy consumption significantly reduces PAN in remote regions (up to 30 %) with commensurate reductions in background NOx.

  10. Directionality of electron-transfer reactions in photosystem I of prokaryotes: universality of the bidirectional electron-transfer model.

    PubMed

    Santabarbara, Stefano; Kuprov, Ilya; Poluektov, Oleg; Casal, Antonio; Russell, Charlotte A; Purton, Saul; Evans, Michael C W

    2010-11-25

    The electron-transfer (ET) reactions in photosystem I (PS I) of prokaryotes have been investigated in wild-type cells of the cyanobacterium Synechocystis sp. PCC 6803, and in two site-directed mutants in which the methionine residue of the reaction center subunits PsaA and PsaB, which acts as the axial ligand to the primary electron chlorophyll acceptor A(0), was substituted with histidine. Analysis by pulsed electron paramagnetic resonance spectroscopy at 100 K indicates the presence of two forms of the secondary spin-correlated radical pairs, which are assigned to [P(700)(+)A(1A)(-)] and [P(700)(+)A(1B)(-)], where A(1A) and A(1B) are the phylloquinone molecules bound to the PsaA and the PsaB reaction center subunits, respectively. Each of the secondary radical pair forms is selectively observed in either the PsaA-M688H or the PsaB-M668H mutant, whereas both radical pairs are observed in the wild type following reduction of the iron-sulfur cluster F(X), the intermediate electron acceptor between A(1) and the terminal acceptors F(A) and F(B). Analysis of the time and spectral dependence of the light-induced electron spin echo allows the resolution of structural differences between the [P(700)(+)A(1A)(-)] and [P(700)(+)A(1B)(-)] radical pairs. The interspin distance is 25.43 ± 0.01 Å for [P(700)(+)A(1A)(-)] and 24.25 ± 0.01 Å for [P(700)(+)A(1B)(-)]. Moreover, the relative orientation of the interspin vector is rotated by ~60° with respect to the g-tensor of the P(700)(+) radical. These estimates are in agreement with the crystallographic structural model, indicating that the cofactors bound to both reaction center subunits of prokaryotic PS I are actively involved in electron transport. This work supports the model that bidirectionality is a general property of type I reaction centers from both prokaryotes and eukaryotes, and contrasts with the situation for photosystem II and other type II reaction centers, in which ET is strongly asymmetric. A revised model

  11. Electrocatalytic oxygen reduction reaction on perovskite oxides: series versus direct pathway.

    PubMed

    Poux, Tiphaine; Bonnefont, Antoine; Kéranguéven, Gwénaëlle; Tsirlina, Galina A; Savinova, Elena R

    2014-07-21

    The mechanism of the oxygen reduction reaction (ORR) on LaCoO(3) and La(0.8)Sr(0.2)MnO(3) perovskite oxides is studied in 1 M NaOH by using the rotating ring disc electrode (RRDE) method. By combining experimental studies with kinetic modeling, it was demonstrated that on perovskite, as well as on perovskite/carbon electrodes, the ORR follows a series pathway through the intermediate formation of hydrogen peroxide. The escape of this intermediate from the electrode strongly depends on: 1) The loading of perovskite; high loadings lead to an overall 4 e(-) oxygen reduction due to efficient hydrogen peroxide re-adsorption on the active sites and its further reduction. 2) The addition of carbon to the catalytic layer, which affects both the utilization of the perovskite surface and the production of hydrogen peroxide. 3) The type of oxide; La(0.8)Sr(0.2)MnO(3) displays higher (compared to LaCoO(3)) activity in the reduction of oxygen to hydrogen peroxide and in the reduction/oxidation of the latter.

  12. Direct detection of Bacillus anthracis DNA in animals by polymerase chain reaction.

    PubMed Central

    Makino, S I; Iinuma-Okada, Y; Maruyama, T; Ezaki, T; Sasakawa, C; Yoshikawa, M

    1993-01-01

    Bacillus anthracis is a soil pathogen capable of causing anthrax. To establish a method for specifically detecting B. anthracis for practical applications, such as for the inspection of slaughterhouses, the cap region, which is essential for encapsulation in B. anthracis, was used in a DNA hybridization study by polymerase chain reaction (PCR). Oligonucleotide primers were designed to amplify a 288-bp DNA fragment within the capA gene by PCR. The amplified DNA sequence specifically hybridized to the DNA of B. anthracis but not to that of other bacterial strains tested. Since this PCR-based method efficiently and specifically detected the capA sequence of bacteria in blood and spleen samples of mice within 8 h after the administration of live B. anthracis, this PCR system could be used for practical applications. By using lysis methods in preparing the samples for PCR, it was possible to amplify the 288-bp DNA segment from samples containing very few bacteria, as few as only 1 sporeforming unit, indicating that the PCR detection method developed in this study will permit the monitoring of B. anthracis contamination in the environment. Images PMID:8458949

  13. Multiple Reaction Monitoring for Direct Quantitation of Intact Proteins Using a Triple Quadrupole Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Wang, Evelyn H.; Combe, Peter C.; Schug, Kevin A.

    2016-05-01

    Methods that can efficiently and effectively quantify proteins are needed to support increasing demand in many bioanalytical fields. Triple quadrupole mass spectrometry (QQQ-MS) is sensitive and specific, and it is routinely used to quantify small molecules. However, low resolution fragmentation-dependent MS detection can pose inherent difficulties for intact proteins. In this research, we investigated variables that affect protein and fragment ion signals to enable protein quantitation using QQQ-MS. Collision induced dissociation gas pressure and collision energy were found to be the most crucial variables for optimization. Multiple reaction monitoring (MRM) transitions for seven standard proteins, including lysozyme, ubiquitin, cytochrome c from both equine and bovine, lactalbumin, myoglobin, and prostate-specific antigen (PSA) were determined. Assuming the eventual goal of applying such methodology is to analyze protein in biological fluids, a liquid chromatography method was developed. Calibration curves of six standard proteins (excluding PSA) were obtained to show the feasibility of intact protein quantification using QQQ-MS. Linearity (2-3 orders), limits of detection (0.5-50 μg/mL), accuracy (<5% error), and precision (1%-12% CV) were determined for each model protein. Sensitivities for different proteins varied considerably. Biological fluids, including human urine, equine plasma, and bovine plasma were used to demonstrate the specificity of the approach. The purpose of this model study was to identify, study, and demonstrate the advantages and challenges for QQQ-MS-based intact protein quantitation, a largely underutilized approach to date.

  14. Numerical study of the process parameters in spark plasma sintering (sps)

    NASA Astrophysics Data System (ADS)

    Chowdhury, Redwan Jahid

    Spark plasma sintering (SPS) is one of the most widely used sintering techniques that utilizes pulsed direct current together with uniaxial pressure to consolidate a wide variety of materials. The unique mechanisms of SPS enable it to sinter powder compacts at a lower temperature and in a shorter time than the conventional hot pressing, hot isostatic pressing and vacuum sintering process. One of the limitations of SPS is the presence of temperature gradients inside the sample, which could result in non-uniform physical and microstructural properties. Detailed study of the temperature and current distributions inside the sintered sample is necessary to minimize the temperature gradients and achieve desired properties. In the present study, a coupled thermal-electric model was developed using finite element codes in ABAQUS software to investigate the temperature and current distributions inside the conductive and non-conductive samples. An integrated experimental-numerical methodology was implemented to determine the system contact resistances accurately. The developed sintering model was validated by a series of experiments, which showed good agreements with simulation results. The temperature distribution inside the sample depends on some process parameters such as sample and tool geometry, punch and die position, applied current and thermal insulation around the die. The role of these parameters on sample temperature distribution was systematically analyzed. The findings of this research could prove very useful for the reliable production of large size sintered samples with controlled and tailored properties.

  15. Enhanced Sintering Kinetics in Aluminum Alloy Powder Consolidated Using DC Electric Fields

    NASA Astrophysics Data System (ADS)

    McWilliams, Brandon; Yu, Jian; Kellogg, Frank; Kilczewski, Steven

    2017-02-01

    Direct current (DC) electric currents were applied during sintering of aluminum alloy (AA5083) green powder compacts and it was found that the kinetics of sintering were greatly enhanced compared to samples processed without a field. In situ sintering kinetics during pressure-less sintering employing electric field strengths and amperages ranging from 0 to 56 V/cm and 0 to 3 A were quantified using digital image correlation. It was found that the application of a DC field during sintering results in a discontinuous change in volume at a critical temperature along with a transition in electrical properties of the compact from insulating to conductive. This effect is similar to the phenomena observed in the flash sintering process currently being actively researched for ceramic powder processing. The temperature at which the flash event occurs was found to be field strength dependent and doubling the field strength was found to decrease the flash temperature by 25 pct. Joule heating of the specimen was measured using thermal imaging and it was found to not contribute enough additional thermal energy to account for the substantially increased sintering rates observed in specimens processed using electric fields.

  16. Field assisted sintering of dense Al-substituted cubic phase Li7La3Zr2O12 solid electrolytes

    NASA Astrophysics Data System (ADS)

    Zhang, Yanhua; Chen, Fei; Tu, Rong; Shen, Qiang; Zhang, Lianmeng

    2014-12-01

    High performance lithium ion conducting Li7La3Zr2O12 solid electrolytes are prepared for the first time by field assisted sintering technology (FAST). The effect of sintering temperature on the phase compositions, microstructure and Li ionic conductivity is systematically investigated. The results show that pure cubic phase LLZO can be obtained at a range of temperatures from 1100 to 1180 °C for no more than 10 min. For the sample sintered at 1150 °C, a maximum relative density of 99.8% with a total ionic conductivity as high as 5.7 × 10-4 S cm-1 are obtained at room temperature. This value is the highest among the present research. Compared with the traditional preparation methods, the current FAST is very promising to obtain high performance LLZO for its advantages of very short sintering time, a single preparation step of reaction-densification processing, and relatively lower sintering temperature.

  17. Use of Direct Dynamics Simulations to Determine Unimolecular Reaction Paths and Arrhenius Parameters for Large Molecules.

    PubMed

    Yang, Li; Sun, Rui; Hase, William L

    2011-11-08

    In a previous study (J. Chem. Phys.2008, 129, 094701) it was shown that for a large molecule, with a total energy much greater than its barrier for decomposition and whose vibrational modes are harmonic oscillators, the expressions for the classical Rice-Ramsperger-Kassel-Marcus (RRKM) (i.e., RRK) and classical transition-state theory (TST) rate constants become equivalent. Using this relationship, a molecule's unimolecular rate constants versus temperature may be determined from chemical dynamics simulations of microcanonical ensembles for the molecule at different total energies. The simulation identifies the molecule's unimolecular pathways and their Arrhenius parameters. In the work presented here, this approach is used to study the thermal decomposition of CH3-NH-CH═CH-CH3, an important constituent in the polymer of cross-linked epoxy resins. Direct dynamics simulations, at the MP2/6-31+G* level of theory, were used to investigate the decomposition of microcanonical ensembles for this molecule. The Arrhenius A and Ea parameters determined from the direct dynamics simulation are in very good agreement with the TST Arrhenius parameters for the MP2/6-31+G* potential energy surface. The simulation method applied here may be particularly useful for large molecules with a multitude of decomposition pathways and whose transition states may be difficult to determine and have structures that are not readily obvious.

  18. Direct synthesis of thermochromic VO{sub 2} through hydrothermal reaction

    SciTech Connect

    Alie, David; Gedvilas, Lynn; Wang, Zhiwei; Tenent, Robert; Engtrakul, Chaiwat; Yan, Yanfa; Shaheen, Sean E.; Dillon, Anne C.; Ban, Chunmei

    2014-04-01

    Thermochromic VO{sub 2} was directly synthesized using hydrothermal techniques. The effects of formation conditions on the structure and morphology of the final product were studied through X-ray diffraction (XRD), and scanning electron microscopy (SEM). Unique hollow sphere morphology was observed for the synthesized VO{sub 2} powders. Ex-situ XRD studies after heat treatment confirmed the thermal stability of the VO{sub 2} structure. Thermochromic properties, as a consequence of the reversible structural transformation between monoclinic VO{sub 2} and tetragonal phases, were observed by Fourier transform infrared spectroscopy (FTIR). - Graphical abstract: Thermochromic VO{sub 2} crystals with hollow spherical and asterisk shape were directly synthesized using hydrothermal techniques. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) studies confirmed the thermal stability and the reversible thermochromic properties of the VO{sub 2} structure. - Highlights: • One-step synthesis of thermochromic VO{sub 2} monoclinic phase, and VO{sub 2} (A and B phases) using hydrothermal technique. VO{sub 2} (A), VO{sub 2} (B). • Identification of the relationship between synthesis conditions and the morphology/structure of the final products. • Formation of VO{sub 2} monoclinic phase with an interesting hollow sphere shape. • Demonstration of superior thermal stability of the VO{sub 2} monoclinic phase. • Characterizing the thermochromic properties of VO{sub 2} monoclinic phase.

  19. Direct determination of enzyme kinetic parameters from single reactions using a new progress curve analysis tool.

    PubMed

    Bäuerle, Felix; Zotter, Agnes; Schreiber, Gideon

    2016-10-15

    With computer-based data-fitting methods becoming a standard tool in biochemistry, progress curve analysis of enzyme kinetics is a feasible, yet seldom used tool. Here we present a versatile Matlab-based tool (PCAT) to analyze catalysis progress curves with three complementary model approaches. The first two models are based on the known closed-form solution for this problem: the first describes the required Lambert W function with an analytical approximation and the second provides a numerical solution of the Lambert W function. The third model is a direct simulation of the enzyme kinetics. Depending on the chosen model, the tools excel in speed, accuracy or initial value requirements. Using simulated and experimental data, we show the strengths and pitfalls of the different fitting models. Direct simulation proves to have the highest level of accuracy, but it also requires reasonable initial values to converge. Finally, we propose a standard procedure to obtain optimized enzyme kinetic parameters from single progress curves.

  20. Microstructure and properties of platelet-reinforced ceramics formed by the directed reaction of zirconium with boron carbide

    SciTech Connect

    Claar, T.D.; Johnson, W.B.; Andersson, C.A.; Schiroky, G.H.

    1989-08-01

    A new family of platelet-reinforced ceramics has been developed using the DIMOX (directed-metal oxidation) process. These materials consist of a metal carbide matrix reinforced with metal diboride platelets and a residual metal phase. Microstructure/property relationships are presented for the ZrB2/ZrC(x)/Zr system, which is formed by the directed reaction of molten zirconium with boron carbide. The metal content can be varied to tailor the mechanical, physical, and thermal properties. These platelet-reinforced ceramics exhibit an attractive combination of high strength (800-1030 MPa), high fracture toughness (11-23 MPa sq rt m), and high thermal conductivity (50-70 W/m K). The effects of the platelet and metal phases on the toughness and fracture behavior are shown. Engineering properties are presented and discussed relative to potential applications. 9 refs.