Copolymerization of ε-caprolactone with Epichlorohydrin by a Green Catalyst, Maghnite

Directory of Open Access Journals (Sweden)

Abdelghani Bouchama

2012-06-01

Full Text Available Most of the cationic initiators used in the synthesis of copolymers are expensive. They may be poisoned by products of the reaction or impurities present in the monomer feed, and contain heavy metals, such as chromium, mercury, antimony, etc., that presents environmental disposal problems for the user. Maghnite is a montmorillonite sheet silicate clay that is exchanged with protons to produce Maghnite-H+ (Mag-H+. This non-toxic and cheaper cationic catalyst was used for the copolymerization of ε-caprolactone (CL with epichlorohydrin (ECH. The effects of the amounts of Mag-H+ and the temperature on the synthesis of poly (ε-caprolactone-co-epichlorohydrin were studied. Increasing Maghnite-H+ proportion and temperature produced the increase in copolymerization yield. The copolymer obtained was characterized by 1H-NMR and IR spectroscopy. Copyright © 2012 BCREC UNDIP. All rights reserved.Received: 24th September 2011, Revised: 12nd December 2011; Accepted: 9th January 2012[How to Cite: A. Bouchama, M.I. Ferrahi, and M. Belbachir. (2012. Copolymerization of ε-caprolactone with Epichlorohydrin by a Green Catalyst, Maghnite. Bulletin of Chemical Reaction Engineering & Catalysis, 7 (1: 43-48.  doi:10.9767/bcrec.7.1.1211.43-48][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.1.1211.43-48 ] | View in 

Predominant 1,2-insertion of styrene in the Pd-catalyzed alternating copolymerization with carbon monoxide.

Science.gov (United States)

Nozaki, K; Komaki, H; Kawashima, Y; Hiyama, T; Matsubara, T

2001-01-31

The regioselectivity of styrene insertion to an acyl-Pd bond was studied by NMR in (i) a stoichiomeric reaction and (ii) a copolymerization with CO. In the stoichiometric reaction of styrene with [(CH(3)CO)Pd(CH(3)CN)[(R,S)-BINAPHOS

Cobaltoporphyrin-Catalyzed CO 2 /Epoxide Copolymerization: Selectivity Control by Molecular Design

KAUST Repository

Anderson, Carly E.; Vagin, Sergei I.; Xia, Wei; Jin, Hanpeng; Rieger, Bernhard

2012-01-01

A series of cobalt(III) chloride porphyrin complexes of the general formula 5,10,15,20-tetra(p-alkoxy)phenylporphyrin cobalt chloride (4b-e) and the related 5,10,15,20-tetra(p-nitro)phenylporphyrin cobalt chloride (4f) are presented and their reactivity toward propylene oxide (PO)/CO 2 coupling/copolymerization is explored. While the nitro-substituted complex (4f), in conjunction with an onium salt, shows moderate activity toward cyclization, the 4b-e/onium systems show superior copolymerization activity in comparison to tetraphenylporphyrin Co(III) chloride (4a) with high selectivity and conversion to poly(propylene carbonate) (PPC). A comprehensive copolymerization behavior study of the alkoxy-substituted porphyrin complexes 4b-e in terms of reaction temperature and CO 2 pressure is presented. Complexes bearing longer alkoxy-substituents demonstrate the highest polymerization activity and molecular weights, however all substituted catalyst systems display a reduced tolerance to increased temperature with respect to PPC formation. Studies of the resulting polymer microstructures show excellent head-to-tail epoxide incorporation and near perfectly alternating poly(carbonate) character at lower polymerization temperatures. © 2012 American Chemical Society.

Cobaltoporphyrin-Catalyzed CO 2 /Epoxide Copolymerization: Selectivity Control by Molecular Design

KAUST Repository

Anderson, Carly E.

2012-09-11

A series of cobalt(III) chloride porphyrin complexes of the general formula 5,10,15,20-tetra(p-alkoxy)phenylporphyrin cobalt chloride (4b-e) and the related 5,10,15,20-tetra(p-nitro)phenylporphyrin cobalt chloride (4f) are presented and their reactivity toward propylene oxide (PO)/CO 2 coupling/copolymerization is explored. While the nitro-substituted complex (4f), in conjunction with an onium salt, shows moderate activity toward cyclization, the 4b-e/onium systems show superior copolymerization activity in comparison to tetraphenylporphyrin Co(III) chloride (4a) with high selectivity and conversion to poly(propylene carbonate) (PPC). A comprehensive copolymerization behavior study of the alkoxy-substituted porphyrin complexes 4b-e in terms of reaction temperature and CO 2 pressure is presented. Complexes bearing longer alkoxy-substituents demonstrate the highest polymerization activity and molecular weights, however all substituted catalyst systems display a reduced tolerance to increased temperature with respect to PPC formation. Studies of the resulting polymer microstructures show excellent head-to-tail epoxide incorporation and near perfectly alternating poly(carbonate) character at lower polymerization temperatures. © 2012 American Chemical Society.

Mechanistic aspects of the metal catalyzed alternating copolymerization of epoxides and carbon monoxide.

Science.gov (United States)

Allmendinger, Markus; Molnar, Ferenc; Zintl, Manuela; Luinstra, Gerrit A; Preishuber-Pflügl, Peter; Rieger, Bernhard

2005-09-05

The cobalt-catalyzed alternating copolymerization of epoxides and CO is a novel, direct approach to aliphatic polyesters, such as poly(hydroxybutyrate) (PHB). This reaction was found to be catalyzed by Ph3Si[Co(CO)4] (4) and pyridine affording in a first step the stable mono-insertion product Ph3Si-O-CH(CH3)-CH2-CO-Co(CO)4 (5). However, a profound mechanistic understanding, especially of the role of pyridine as the key component for the polymerization reaction was missing. ATR-IR online monitoring under catalytic conditions and DFT calculations were used to show that an acylpyridinium cation is formed by cleavage of the cobalt-acyl bond of 5 in the presence of pyridine. The Lewis acid thus generated activates the next incoming epoxide monomer for ring opening through [Co(CO)4]-. The catalytic cycle is completed by a subsequent CO insertion in the new cobalt-alkyl bond. The calculations are used to explore the energetic hypersurface of the polymerization reaction and are complemented by extended experimental investigations that also support the mechanistic hypotheses.

Radiation induced graft copolymerization of acrylamide onto poly (3-hydroxybutyrate)

International Nuclear Information System (INIS)

Gonzalez Torres, Maykel; Rapado Paneque, Manuel; Paredes Zaldivar, Mayte; Altanes Valentin, Sonia; Barrera Gonzalez, Gisela

2008-01-01

The graft copolymer poly (3-hydroxybutyrate)-g- polyacrylamide [P (HB-g-AAm)] was synthesized by radiation induced graft copolymerization of acrylamide onto poly (3-hydroxybutyrate). The study was conducted by the simultaneous irradiation method. The structure of [P (HB-g-AAm)] was identified by Fourier Transform Infrared (FTIR) spectroscopy. Thermal behavior of the graft copolymer was also studied by Thermal Gravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC). From the results it was found that FTIR studies showed new signals (stretching -N-H) as strong evidence of grafting. The grafting degree was found to be 10 % and the thermodynamic parameter obtained from the DSC thermogram of plain PHB and the graft copolymer varied showing decrease in the material crystallinity and increase in the glass transition temperature. These results demonstrate that the radiation induced graft copolymerization reaction of acrylamide onto PHB was successively achieved. (Author)

Copper mediated controlled radical copolymerization of styrene and2-ethylhexyl acrylate and determination of their reactivity ratios.

Directory of Open Access Journals (Sweden)

Bishnu Prasad Koiry

2014-10-01

Full Text Available Copolymerization is an important synthetic tool to prepare polymers with desirable combination of properties which are difficult to achieve from the different homopolymers concerned. This investigation reports the copolymerization of 2-ethylhexyl acrylate (EHA and styrene using copper bromide (CuBr as catalyst in combination with N,N,N’,N,N- pentamethyldiethylenetriamine (PMDETA as ligand and 1-phenylethyl bromide (PEBr as initiator. Linear kinetic plot and linear increase in molecular weights versus conversion indicate that copolymerization reactions were controlled. The copolymer composition was calculated using 1H NMR studies. The reactivity ratio of styrene and EHA (r1 and r2 were determined using the Finemann-Ross (FR, inverted Finemann-Ross (FR and Kelen-Tudos (KT methods. Thermal properties of the copolymers were also studied by using TGA and DSC analysis.

Extraction of palm tree cellulose and its functionalization via graft copolymerization.

Science.gov (United States)

Al-Hoqbani, Abdulmajeed A; Abdel-Halim, E S; Al-Deyab, Salem S

2014-09-01

The work in this paper was planned with the aim of extracting the cellulosic component of palm tree waste and functionalizing this cellulose through graft copolymerization with acrylic acid. The cellulose extraction included hot alkali treatment with aqueous sodium hydroxide to remove the non-cellulosic binding materials. The alkali treatment was followed by an oxidative bleaching using peracid/hydrogen peroxide mixture with the aim of removing the rest of non-cellulosic materials to improve the fiber hydrophilicity and accessibility towards further grafting reaction. Optimum conditions for cellulose extraction are boiling in 5% (W/V) NaOH in a material to liquor ratio of 1:20 for 1 h then bleaching with 60 ml/l bleaching mixture at initial pH value of 6.5 for 30 min. The pH of the bleaching medium is turned to the alkaline range 11 and bleaching continues for extra 30 min. Graft copolymerization reaction was initiated by potassium bromate/thiourea dioxide redox system. Optimum conditions for grafting are 30 mmol of potassium bromate, 30 mmol of thiourea dioxide and 150 g of acrylic acid (each per 100 g of cellulose). The polymerization reaction was carried out for 120 min at 50°C using a material to liquor ratio of 1:20. Copyright © 2014 Elsevier B.V. All rights reserved.

Mechanism of alternating copolymerization of methyl methacrylate with styrene in the presence of diethylaluminum chloride

International Nuclear Information System (INIS)

Zubov, V.P.; Lachinov, M.B.; Ignatova, E.V.; Georgiev, G.S.; Golubev, V.B.; Kabanov, V.A.

1982-01-01

A kinetic study of the propagation mechanism of the alternating copolymerization of styrene (St) with methyl methacrylate (MMA) in the presence of a complexing agent (diethylaluminum chloride, DEAC) in bulk and in tetrachloroethylene solutions at a molar ratio DEAC/MMA = 0.5 has been carried out. It has been shown that the copolymerization is a chain radical process characterized by a short active-center lifetime, bimolecular termination, and high rate of chain transfer to the complexed MMA. A kinetic scheme has been proposed for the propagation mechanism of alternating copolymerization in the presence of a complexing agent not requiring independent measurements of the equilibrium constant of complexation. It has been found that spontaneous and uv-initiated copolymerizations in the system have different mechanisms of initiation and a common mechanism of propagation. The propagation proceeds by addition of single monomers as well as donor-acceptor complexes of the comonomers to the propagation radicals, with the first mechanism being predominant. Inclusion of the monomers in the complex leads to an increase of the St reactivity and to a decrease of the MMA reactivity in propagation to the corresponding macroradicals in comparison with the reactivity of the free monomers. A number of kinetic and statistical parameters of the propagation reaction have been calculated

Radiation graft copolymerization of n-butyl acrylate on natural rubber latex

International Nuclear Information System (INIS)

Sundardi, F.; Kadariah, S.

1986-01-01

A method of radiation graft copolymerization of n-butyl acrylate (NBA) on natural rubber (NR) latex has been studied. The rate of conversion increases with the increase of NBA in latex. An irradiation dose of about 12 kGy is needed to obtain 90% conversion with 40 phr of NBA in latex. Tensile strength, tear strength, and elongation at break of grafted NR are found to decrease with increasing degree of grafting. The physical strength of a vulcanizate prepared from a mixture of NR and ply-NBA was found to be better than that of NBA-NR graft copolymer vulcanizate. The graft copolymerization reaction takes place in the outer layer of NR particles, and because the secondary bonds between poly-NBA molecules may be weaker than those between NR molecules, the existence of a poly-NBA layer in NR particles will decrease its physical strength

Chemoselective alternating copolymerization of limonene dioxide and carbon dioxide : a new highly functional aliphatic epoxy polycarbonate

NARCIS (Netherlands)

Li, C.; Sablong, R.J.; Koning, C.E.

The alternating copolymerization of biorenewable limonene dioxide with carbon dioxide (CO2) catalyzed by a zinc β-diiminate complex is reported. The chemoselective reaction results in linear amorphous polycarbonates that carry pendent methyloxiranes and exhibit glass transition temperatures (Tg) up

Synthesis of Terpolymers with Homogeneous Composition by Free Radical Copolymerization of Maleic Anhydride, Perfluorooctyl and Butyl or Dodecyl Methacrylates: Application of the Continuous Flow Monomer Addition Technique

Directory of Open Access Journals (Sweden)

Marian Szkudlarek

2017-11-01

Full Text Available Terpolymers of homogeneous composition were prepared by free radical copolymerization of butyl or dodecyl methacrylate, 1H,1H,2H,2H-perfluorodecyl methacrylate and maleic anhydride using the continuous monomer addition technique. The copolymerization reactions were performed at 65 °C in the presence of azobisisobutyronitrile as an initiator in a mixture of methyl ethyl ketone and 1,3-bis (trifluoromethylbenzene. The monomers and initiator are added to the reaction mixture with the same rate they are consumed in 5- and 10-fold excess compared to the initial monomer stock. The obtained terpolymers with molecular weights Mn = 50,000–70,000 are of uniform composition, close to the composition determined in low conversion experiments, proving the principle of the chosen concept. The kinetic data necessary for the design of the continuous addition experiment were obtained from binary copolymerization experiments at low monomer conversion (to avoid compositional drift. In addition, the so-called terpolymerization parameter was determined from ternary copolymerization experiments.

Electrochemical copolymerization of thiophene derivatives; a precursor to photovoltaic devices

International Nuclear Information System (INIS)

Kumar, Prajwal; Ranjith, K.; Gupta, Satyajit; Ramamurthy, Praveen C.

2011-01-01

Highlights: → This work presents an electrochemical technique for the polymerization and copolymerization of thiophene derivatives. → Copolymerization of thiophene based monomers like 7,9-dithiophene-2yl-8H-cyclopenta[a]acenaphthalene-8-one and 3-hexylthiophene are synthesized. → Study of the structural, optical, thermal, conductivity, morphological, band gap and impedance measurements of the copolymer indicates a suitable material for photovoltaic applications. - Abstract: This work presents an electrochemical technique for the polymerization and copolymerization of thiophene derivatives like 7,9-dithiophene-2yl-8H-cyclopenta[a]acenaphthalene-8-one and 3-hexylthiophene. The structural characterization of chemically synthesized monomers and electrochemically synthesized polymers was carried out by nuclear magnetic resonance and Fourier transform infrared spectroscopy. Thermal characterizations indicate that copolymer has increased thermal stability than that of homopolymer. Morphological studies of the polymerized films carried out by scanning electron microscopy shows network structure of copolymer. Optical properties of the homopolymers and copolymer were studied by UV-visible spectrometer and it was observed that band gap of copolymer is less than the homopolymers. HOMO and LUMO levels, band gap values of the respective polymers were also calculated from the cyclic voltammetry technique with various scan rates. By the peak current obtained from various scan rates shows that all polymerization reactions are diffusion controlled process. Charge transfer resistances of polymers were determined using Nyquist plots. Conductivity of synthesized polymers shows higher conductivity for copolymer than homopolymers.

Radiation initiated copolymerization of allyl alcohol with acrylonitrile

International Nuclear Information System (INIS)

Solpan, Dilek; Guven, Olgun

1996-01-01

Copolymerization of allyl alcohol (AA) with acrylonitrile (AN) initiated by γ-rays has been investigated to determine the respective reactivity ratios. Three different experimental techniques, namely Fourier Transform Infrared (FTIR), Ultraviolet (UV/vis) and elemental analysis (EA) have been used for the determination of copolymer compositions. Fineman-Ross (FR), Kelen-Tudos (KT), Non-Linear Least Square (NLLS) Analysis and Q-e methods have been applied to the three sets of experimental data. It has been concluded that data obtained from elemental analysis as applied to the Non-Linear Least Square approach gave the most reliable reactivity ratios as 2.09 and 0.40 for acrylonitrile and allyl alcohol, respectively. (Author)

Palladium/IzQO-Catalyzed Coordination-Insertion Copolymerization of Ethylene and 1,1-Disubstituted Ethylenes Bearing a Polar Functional Group.

Science.gov (United States)

Yasuda, Hina; Nakano, Ryo; Ito, Shingo; Nozaki, Kyoko

2018-02-07

Coordination-insertion copolymerization of ethylene with 1,1-disubstituted ethylenes bearing a polar functional group, such as methyl methacrylate (MMA), is a long-standing challenge in catalytic polymerization. The major obstacle for this process is the huge difference in reactivity of ethylene versus 1,1-disubstituted ethylenes toward both coordination and insertion. Herein we report the copolymerization of ethylene and 1,1-disubstituted ethylenes by using an imidazo[1,5-a]quinolin-9-olate-1-ylidene-supported palladium catalyst. Various types of 1,1-disubstituted ethylenes were successfully incorporated into the polyethylene chain. In-depth characterization of the obtained copolymers and mechanistic inferences drawn from stoichiometric reactions of alkylpalladium complexes with methyl methacrylate and ethylene indicate that the copolymerization proceeds by the same coordination-insertion mechanism that has been postulated for ethylene.

Automated batch emulsion copolymerization of styrene and butyl acrylate

NARCIS (Netherlands)

Mballa Mballa, M.A.; Schubert, U.S.; Heuts, J.P.A.; Herk, van A.M.

2011-01-01

This article describes a method for carrying out emulsion copolymerization using an automated synthesizer. For this purpose, batch emulsion copolymerizations of styrene and butyl acrylate were investigated. The optimization of the polymerization system required tuning the liquid transfer method,

Kinetic investigations of graft copolymerization of sodium styrene sulfonate onto electron beam irradiated poly(vinylidene fluoride) films

Energy Technology Data Exchange (ETDEWEB)

Mahmoud Nasef, Mohamed, E-mail: mahmoudeithar@fkkksa.utm.m [Institute of Hydrogen Economy, International City Campus, Universiti Teknologi Malaysia, Jalan Semarak, 54100 Kuala Lumpur (Malaysia); Chemical Engineering Department, Faculty of Chemical and Natural Resources Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor (Malaysia); Saidi, Hamdani [Institute of Hydrogen Economy, International City Campus, Universiti Teknologi Malaysia, Jalan Semarak, 54100 Kuala Lumpur (Malaysia); Chemical Engineering Department, Faculty of Chemical and Natural Resources Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor (Malaysia); Mohd Dahlan, Khairul Zaman [Radiation Processing Technology Division, Malaysian Nuclear Agency, Bangi, 43000 Kajang, Selangor (Malaysia)

2011-01-15

Graft copolymerization of sodium styrene sulfonate (SSS) onto electron beam (EB) irradiated poly(vinylidene fluoride) (PVDF) films was investigated to find out a simple preparation process for sulfonic acid proton exchange membranes with respect to monomer concentration, absorbed dose, temperature, film thickness and storage time. The reaction order of the monomer concentration and absorbed dose of grafting was found to be 2.84 and 1.20, respectively. The overall activation energy for graft copolymerization reaction was calculated to be 11.36 kJ/mol. The initial rate of grafting was found to decrease with an increase in the film thickness. The trapped radicals in the irradiated PVDF films remained effective in initiating the reaction without considerable loss in grafting level up to 180 days, when stored under -60 {sup o}C. The presence and distribution of polystyrene sulfonate grafts in the obtained membranes were observed by Fourier transform infrared (FTIR) spectroscopic analysis, scanning optical microscope and scanning transmission electron microscopy (STEM) coupled with X-ray energy dispersive (EDX), respectively.

Radiation-induced copolymerization of hexafluoroacetone with α-olefins

International Nuclear Information System (INIS)

Matsuda, O.; Watanabe, S.; Okamoto, J.; Machi, S.; Tabata, Y.

1977-01-01

The copolymerization of hexafluoroacetone with higher α-olefins above butene, such as 1-pentene (I), 1-hexene (II), 1-octene (III), 2-methyl-1-butene (IV), 2-methyl-1-pentene (V), 3-methyl-1-butene (VI), and 4-methyl-1-pentene (VII) was studied at relatively low temperatures by γ-ray irradiation. Copolymerization of II, IV, V, and VII with hexafluoroacetone was found to scarcely take place at -78 0 C in bulk, but the addition of trichlorotrifluoroethane in amounts to yield equimolar mixtures resulted in conversion of 15.7 percent for IV and of 2.1 to 4.0 percent for the other α-olefins. Higher conversion of V at -78 0 C than at 0 0 C suggest that copolymerization may take place via an ionic mechanism. The effects of various additives on the copolymerization are reported. Infrared spectral studies indicated that the double bond of the α-olefins is opened to form a polymer. The C--O double bond of the hexafluoroacetone and the α-olefin double bond are opened to form the copolymer

High-pressure copolymerization of C 2H 4 and CO

Science.gov (United States)

Buback, M.; Tups, H.

1986-05-01

Kinetics of the free radical high-pressure copolymerization of ethylene and carbon monoxide using thermal, chemical, and laser-photochemical initiation have been investigated via quantitative infrared and near infrared spectroscopy up to 2300 bar and 513 K. The slow thermal copolymerization is influenced by the formation of metal carbonyls inside the stainless steel cell. With chemical initiation, using 120 ppm oxygen, ethylene and CO polymerize to polyketone without any indication of additional products. The photo-copolymerization induced by an exciplex laser working on the KrF line at 248 nm, has been studied between 486 K and 513 K up to 2300 bar and for CO mole fractions up to 3 percent. Overall quantum yields of about 2000 copolymerizing molecules per one absorbed laser photon are observed.

Concerning the Deactivation of Cobalt(III)-Based Porphyrin and Salen Catalysts in Epoxide/CO 2 Copolymerization

KAUST Repository

Xia, Wei

2015-02-05

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Functioning as active catalysts for propylene oxide (PO) and carbon dioxide copolymerization, cobalt(III)-based salen and porphyrin complexes have drawn great attention owing to their readily modifiable nature and promising catalytic behavior, such as high selectivity for the copolymer formation and good regioselectivity with respect to the polymer microstructure. Both cobalt(III)-salen and porphyrin catalysts have been found to undergo reduction reactions to their corresponding catalytically inactive cobalt(II) species in the presence of propylene oxide, as evidenced by UV/Vis and NMR spectroscopies and X-ray crystallography (for cobalt(II)-salen). Further investigations on a TPPCoCl (TPP=tetraphenylporphyrin) and NaOMe system reveal that such a catalyst reduction is attributed to the presence of alkoxide anions. Kinetic studies of the redox reaction of TPPCoCl with NaOMe suggests a pseudo-first order in cobalt(III)-porphyrin. The addition of a co-catalyst, namely bis(triphenylphosphine)iminium chloride (PPNCl), into the reaction system of cobalt(III)-salen/porphyrin and PO shows no direct stabilizing effect. However, the results of PO/CO2 copolymerization by cobalt(III)-salen/porphyrin with PPNCl suggest a suppressed catalyst reduction. This phenomenon is explained by a rapid transformation of the alkoxide into the carbonate chain end in the course of the polymer formation, greatly shortening the lifetime of the autoreducible PO-ring-opening intermediates, cobalt(III)-salen/porphyrin alkoxides. CO2 saves: The deactivation of cobalt(III)-porphyrin and salen catalysts in propylene oxide/carbon dioxide copolymerization is systematically investigated, revealing a proposed mechanism for the catalyst reduction (see scheme).

Concerning the Deactivation of Cobalt(III)-Based Porphyrin and Salen Catalysts in Epoxide/CO 2 Copolymerization

KAUST Repository

Xia, Wei; Salmeia, Khalifah A.; Vagin, Sergei I.; Rieger, Bernhard

2015-01-01

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Functioning as active catalysts for propylene oxide (PO) and carbon dioxide copolymerization, cobalt(III)-based salen and porphyrin complexes have drawn great attention owing to their readily modifiable nature and promising catalytic behavior, such as high selectivity for the copolymer formation and good regioselectivity with respect to the polymer microstructure. Both cobalt(III)-salen and porphyrin catalysts have been found to undergo reduction reactions to their corresponding catalytically inactive cobalt(II) species in the presence of propylene oxide, as evidenced by UV/Vis and NMR spectroscopies and X-ray crystallography (for cobalt(II)-salen). Further investigations on a TPPCoCl (TPP=tetraphenylporphyrin) and NaOMe system reveal that such a catalyst reduction is attributed to the presence of alkoxide anions. Kinetic studies of the redox reaction of TPPCoCl with NaOMe suggests a pseudo-first order in cobalt(III)-porphyrin. The addition of a co-catalyst, namely bis(triphenylphosphine)iminium chloride (PPNCl), into the reaction system of cobalt(III)-salen/porphyrin and PO shows no direct stabilizing effect. However, the results of PO/CO2 copolymerization by cobalt(III)-salen/porphyrin with PPNCl suggest a suppressed catalyst reduction. This phenomenon is explained by a rapid transformation of the alkoxide into the carbonate chain end in the course of the polymer formation, greatly shortening the lifetime of the autoreducible PO-ring-opening intermediates, cobalt(III)-salen/porphyrin alkoxides. CO2 saves: The deactivation of cobalt(III)-porphyrin and salen catalysts in propylene oxide/carbon dioxide copolymerization is systematically investigated, revealing a proposed mechanism for the catalyst reduction (see scheme).

Optimizing the bulk copolymerization of D,L-lactide and glycolide by response surface methodology

Directory of Open Access Journals (Sweden)

J. F. Rodriguez

2013-11-01

Full Text Available Poly(D,L-lactide-co-glycolide, PLGA, is a biodegradable polyester with high interest in medical industry, especially when zinc (II 2-ethylhexanoate (ZnOct2 is used as catalyst substitute in polymerization processes as a substitute of the toxic tin (II 2-ethylhexanoate (SnOct2 together an initiator such as methanol to improve the reaction rate. This article shows the optimization of the bulk copolymerization method by using a factorial design approach on three experimental parameters: temperature (T, molar ratio monomers/catalyst (MC ratio and molar ratio initiator/catalyst (IC ratio. Their influence on mass conversion (X and number-average molecular weight (Mn was also discussed. Also it provides a useful tool to select in a fast way the proper experimental conditions for the obtaining of this polymer as a previous stage in the synthesis and impregnation of biodegradable scaffolds. This analysis revealed that the most relevant variable in the process is the temperature, being desirable to use the high value (160ºC in order to obtain high values of conversion and molecular weight.

Radiation-induced copolymerization of α,β,β-trifluoroacrylonitrile with α-olefin

International Nuclear Information System (INIS)

Matsuda, O.; Kostov, G.K.; Tabata, Y.; Machi, S.

1979-01-01

Homopolymerization and copolymerization of α,β,β-trifluoroacrylonitrile (FAN) with α-olefins were carried out in bulk by γ-ray irradiation at 25 0 C. FAN gives very small quantities of brown and greasy low molecular weight polymer. Cyano groups in FAN polymer were found to be readily hydrolyzed to acid amide groups in the atmosphere. FAN was found to copolymerize with ethylene, propylene, and isobutylene via a radical mechanism to form equimolar copolymers in a wide range of monomer compositions. The polymerization rate increases linearly with FAN fraction in the monomer mixture. These copolymers are also hydrolyzed in the atmosphere, and the hydrolysis proceeds with more difficulty for the copolymer with higher α-olefin. The reactivity ratios r 1 (FAN) and r 2 (α-olefin) were determined to be 0.01 and 0.12 for the FAN/ethylene copolymerization and 0.01 and 0.07 for the FAN/propylene copolymerization. These results confirm that an alternating copolymerization takes place in the FAN/α-olefin system

Complex-radical copolymerization of vinyl monomers on organoelemental initiators

International Nuclear Information System (INIS)

Grishin, D.F.

1993-01-01

Data on regularities of the initiation and growth of the (co)polymerization of polar vinyl series monomers on organo-elemental initiator, organo-boron in particular, are generalized. The effect of organo-metallic compounds and some phenol type inhibitors on the rate of acrylate (co)polymerization is analyzed from view of the change of electroacceptor properties (electrophilicity) of macroradicals

Copolymerization of propene and styrene using a zirconocene - methylaluminoxane initiator system

International Nuclear Information System (INIS)

Rabagliati, F.M.; Rodriguez, F.J.; Quijada, R.; Galland, G.B.

2009-01-01

The copolymerization of propene with styrene has been tested using the rac-Et(Ind) 2 ZrCl 2 -methylaluminoxane initiator system. The various proportion of styrene in initial feed showed an important effect on the polymerization activity. Low contents of styrene in the reaction produced a considerable fall in the activity. Respect to thermal behavior, it is noted that obtained propene/styrene copolymers showed Tm values slightly lower than the corresponding polypropene one. NMR spectroscopy allowed to confirm that the copolymer composition includes a very low incorporation of styrene in polypropylene chains. (author)

Computational Investigation of the Competition between the Concerted Diels-Alder Reaction and Formation of Diradicals in Reactions of Acrylonitrile with Non-Polar Dienes

Science.gov (United States)

James, Natalie C.; Um, Joann M.; Padias, Anne B.; Hall, H. K.; Houk, K. N.

2013-01-01

The energetics of the Diels-Alder cycloaddition reactions of several 1,3-dienes with acrylonitrile, and the energetics of formation of diradicals, were investigated with density functional theory (B3LYP and M06-2X) and compared to experimental data. For the reaction of 2,3-dimethyl-1,3-butadiene with acrylonitrile, the concerted reaction is favored over the diradical pathway by 2.5 kcal/mol using B3LYP/6-31G(d); experimentally this reaction gives both cycloadduct and copolymer. The concerted cycloaddition of cyclopentadiene with acrylonitrile is preferred computationally over the stepwise pathway by 5.9 kcal/mol; experimentally, only the Diels-Alder adduct is formed. For the reactions of (E)-1,3-pentadiene and acrylonitrile, both cycloaddition and copolymerization were observed experimentally; these trends were mimicked by the computational results, which showed only a 1.2 kcal/mol preference for the concerted pathway. For the reactions of (Z)-1,3-pentadiene and acrylonitrile, the stepwise pathway is preferred by 3.9 kcal/mol, in agreement with previous experimental findings that only polymerization occurs. M06-2X is known to give more accurate activation and reaction energetics but the energies of diradicals are too high. PMID:23758325

Radical Copolymerization Kinetics of Bio-Renewable Butyrolactone Monomer in Aqueous Solution

Directory of Open Access Journals (Sweden)

Sharmaine B. Luk

2017-10-01

Full Text Available The radical copolymerization kinetics of acrylamide (AM and the water-soluble monomer sodium 4-hydroxy-4-methyl-2-methylene butanoate (SHMeMB, formed by saponification of the bio-sourced monomer γ-methyl-α-methylene-γ-butyrolactone (MeMBL, are investigated to explain the previously reported slow rates of reaction during synthesis of superabsorbent hydrogels. Limiting conversions were observed to decrease with increased temperature during SHMeMB homopolymerization, suggesting that polymerization rate is limited by depropagation. Comonomer composition drift also increased with temperature, with more AM incorporated into the copolymer due to SHMeMB depropagation. Using previous estimates for the SHMeMB propagation rate coefficient, the conversion profiles were used to estimate rate coefficients for depropagation and termination (kt. The estimate for kt,SHMeMB was found to be of the same order of magnitude as that recently reported for sodium methacrylate, with the averaged copolymerization termination rate coefficient dominated by the presence of SHMeMB in the system. In addition, it was found that depropagation still controlled the SHMeMB polymerization rate at elevated temperatures in the presence of added salt.

Y-shaped Folic Acid-Conjugated PEG-PCL Copolymeric Micelles for Delivery of Curcumin.

Science.gov (United States)

Feng, Runliang; Zhu, Wenxia; Chu, Wei; Teng, Fangfang; Meng, Ning; Deng, Peizong; Song, Zhimei

2017-01-01

Curcumin is a natural hydrophobic product showing anticancer activity. Many studies show its potential use in the field of cancer treatment due to its safety and efficiency. However, its application is limited due to its low water-solubility and poor selective delivery to cancer. A Y-shaped folic acid-modified poly (ethylene glycol)-b-poly (ε-caprolactone)2 copolymer was prepared to improve curcumin solubility and realize its selective delivery to cancer. The copolymer was synthesized through selective acylation reaction of folic acid with α- monoamino poly(ethylene glycol)-b-poly(ε-caprolactone)2. Curcumin was encapsulated into the copolymeric micelles with 93.71% of encapsulation efficiency and 11.94 % of loading capacity. The results from confocal microscopy and cellular uptake tests showed that folic acid-modified copolymeric micelles could improve cellular uptake of curcumin in Hela and HepG2 cells compared with folic acid-unmodified micelles. In vitro cytotoxicity assay showed that folic acid-modified micelles improved anticancer activity against Hela and HepG2 cells in comparison to folic acidunmodified micelles. Meanwhile, both drug-loaded micelles demonstrated higher activity against Hela cell lines than HepG2. The research results suggested that the folic acid-modified Y-shaped copolymeric micelles should be used to enhance hydrophobic anticancer drugs' solubility and their specific delivery to folic acid receptors-overexpressed cancer. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Radiation-induced emulsion copolymerization of vinyl chloride with vinyl acetate in an engineering flow system

International Nuclear Information System (INIS)

Tsai, J.T.; Stahel, E.P.; Stannett, V.T.

1979-01-01

A flow reactor system was used to study the radiation-induced emulsion copolymerization of vinyl chloride with vinyl acetate. The emulsion was recirculated from a stirred vessel through transfer lines to a tubular reactor located within a high-intensity Co-60 source. The effects of physical chemical variables such as soap concentration, phase ratio, reaction temperature and residence time distribution on the molecular weight properties were investigated. The rate of copolymerization was found to be proportional to the 0.17 power of the soap concentration. Variation of the monomer-water ratio produced no significant change in rate. The rate increased with an increase in temperature over the range 5 to 50 0 C, while the average molecular weights of the copolymer increased with decreasing polymerization temperature. The molecular weight distribution in this engineering system was found to be essentially similar to those produced in a batch system

Graft-copolymerization onto carbon black

International Nuclear Information System (INIS)

Nakase, Yoshiaki; Nishii, Masanobu; Kijima, Toshiyuki; Kato, Hiroshi.

1988-07-01

Radiation-induced graft copolymerization of vinyl monomer onto carbon black was performed. During the γ-ray- and electron beam-induced polymerization (In-source), or the electron beam post-polymerization, the graft-copolymerization behavior was affected by the kinds of both carbon blacks and monomers, i.e. the smaller the size of carbon black particles, the higher the apparent grafted fraction. Homopolymer in the grafted carbon black samples was washed out by the solvent of the polymer, and the extracted polymer seemed to be dimer or trimer of the used monomer. In the case of the post-polymerization with the pre-irradiation doses of 50 Mrad, homopolymer was hardly observed. The polymer sheets of plastics or rubbers with grafted carbon black had an electrical conductivity unalterable considerably by the heating cycles. The particles of grafted carbon black in the sheet might be kept much more at the surface layer within 100 nm depth than at the inner layer. (author)

Comparison of Polymer Networks Synthesized by Conventional Free Radical and RAFT Copolymerization Processes in Supercritical Carbon Dioxide

Directory of Open Access Journals (Sweden)

Patricia Pérez-Salinas

2017-05-01

Full Text Available There is a debate in the literature on whether or not polymer networks synthesized by reversible deactivation radical polymerization (RDRP processes, such as reversible addition-fragmentation radical transfer (RAFT copolymerization of vinyl/divinyl monomers, are less heterogeneous than those synthesized by conventional free radical copolymerization (FRP. In this contribution, the syntheses by FRP and RAFT of hydrogels based on 2-hydroxyethylene methacrylate (HEMA and ethylene glycol dimethacrylate (EGDMA in supercritical carbon dioxide (scCO2, using Krytox 157 FSL as the dispersing agent, and the properties of the materials produced, are compared. The materials were characterized by differential scanning calorimetry (DSC, swelling index (SI, infrared spectroscopy (FTIR and scanning electron microscopy (SEM. Studies on ciprofloxacin loading and release rate from hydrogels were also carried out. The combined results show that the hydrogels synthesized by FRP and RAFT are significantly different, with apparently less heterogeneity present in the materials synthesized by RAFT copolymerization. A ratio of experimental (Mcexp to theoretical (Mctheo molecular weight between crosslinks was established as a quantitative tool to assess the degree of heterogeneity of a polymer network.

Structural and behavioral characteristics of radiolytically synthesized polyacrylic acid–polyacrylonitrile copolymeric hydrogels

International Nuclear Information System (INIS)

Bera, Anuradha; Misra, R.K.; Singh, Shailendra K.

2013-01-01

Copolymeric hydrogels of polyacrylic acid (PAA) – polyacrylonitrile (PAN) was radiolytically synthesized from their respective monomers with trimethyloltrimethacrylate (TMPTMA) as the crosslinker wherein both polymerization and crosslinking could be achieved in a single step reaction using 60 Co γ-radiation under varying doses and dose rates. The formation of the hydrogels was confirmed by their FT-IR analysis, while their thermal degradation patterns were investigated through thermogravimetric analysis in both the dry and swelled state. The water sorption studies showed rapid swelling behavior of these hydrogels, where swelling (%EWC) was found to be strongly dependent on the ratio of the two monomers in the hydrogels and the swelling kinetics dependent on the dose rates of hydrogel synthesis. These radiolytically synthesized hydrogels responded to electrical stimulus both in terms of the bending speed as well as bending angle under an applied voltage. The nature of the deformation was reversible and can be controlled through switching the voltage on and off. - Highlights: • Polyacrylic acid – polyacrilonitrile copolymeric hydrogel has been radiolytically synthesized. • Trimethyloltrimethacrylate (TMPTMA) used as crosslinker. • Hydrogel has been characterized and tested for electroresponsive character. • Bending angles and bending speed were found dependent upon applied voltage

Recent advances in photoinduced donor/acceptor copolymerization

International Nuclear Information System (INIS)

Joensson, S.; Viswanathan, K.; Hoyle, C.E.; Clark, S.C.; Miller, C.; Morel, F.; Decker, C.

1999-01-01

Photoinitiated free radical polymerization of donor (D)/acceptor (A) type monomers has gained considerable interest due to the possibility to efficiently photopolymerize non-acrylate based systems. Furthermore, this photoinduced alternating copolymerization can be accomplished without the presence of a conventional free radical generating photoinitiator. In the past, we have shown that the structural influences in the direct photolysis of N-Alkyl and N-Arylmaleimides as well as their corresponding ground state charge transfer complexes (CTC) with suitable donors have carefully been investigated. For certain combinations of A and D type monomers, a direct photolysis of the ground state complex or the excitation of the acceptor, followed by the formation of an exciplex, has been shown to initiate the copolymerization. Herein, we show that the main route of initiation is based on inter or intra molecular H-abstraction from an excited state maleimide, whereby no exciplex formation takes place. H-abstraction will predominantly take place in systems where easily abstractable hydrogens are present. Our laser flash photolysis investigation, ESR (A. Hiroshi, I. Takasi, T. Nosi, Macromol. Chem. 190 (1989) 2821) and phosphorescence emissions (K.S. Chen, T. Foster, J.K.S. Wan, J. Phys. Chem. 84 (1980) 2473; C.J. Seliskar, S.P. McGlynn, J. Chem. Phys. 55 (1971) 4337) studies show that triplet excited states of N-alkyl substituted maleimides (RMI), which are well known strong precursors for direct H-abstractions from aliphatic ethers and secondary alcohols, are formed upon excitation. Rates of copolymerization and degrees of conversion for copolymerization of maleimide/vinyl ether pairs in air and nitrogen have been measured as a function of hydrogen abstractability of the excited triplet state MI as well as the influence of concentration and hydrogen donating effect of the hydrogen donor

Copolymerization of carbon monoxide and styrene catalyzed by resin-supported palladium polymer

Directory of Open Access Journals (Sweden)

2007-02-01

Full Text Available Polyketone was prepared by the copolymerization of carbon monoxide (CO and styrene (ST catalyzed by o-phenylenediamine resin-supported palladium acetate. Effects of each catalytic system component such as 2,2’-bipyridine, 1,4-quinone and p-toluene-sulphonate on the copolymerization were investigated. The resin-supported catalyst and the copolymerization product were characterized by infrared spectroscopy (IR, differential scanning calorimetry (DSC, thermogravimetry (TG, X-ray photoelectron spectroscopy (XPS, Scanning Electron Microscopy (SEM. Results indicated that the resin-supported catalyst has excellent catalytic property. Furthermore, partial catalytic activity was maintained after the catalyst was used for five times.

Chain chemical reactions during matrix devitrification

International Nuclear Information System (INIS)

Barkalov, I.M.

1980-01-01

Investigation results of chain reaction mechanisms, proceeding at devitrification of glass-like matrices under the effect of γ-irradiation are summarized. Peculiarities of kinetics and mechanism of chain reactions proceeding at devitrification are considered: hydrocarbon chlorination, polymerization of vinyl monomers, copolymerization and graft polymerization. Possible application aspects of the chain reaction conducting during matrix devitrification are also considered

Thermosensitive copolymeric hydrogels with the regulated temperature of a phase transition

International Nuclear Information System (INIS)

Samchenko, Yu.M.; Konovalova, V.V.; Korotich, E.I.; Poltoratskaya, T.P.; Pobegaj, A.A.; Burban, A.F.; Ul'berg, Z.R.; Samchenko, Yu.M.; Konovalova, V.V.; Korotich, E.I.; Poltoratskaya, T.P.; Pobegaj, A.A.; Burban, A.F.; Ul'berg, Z.R.

2011-01-01

The work is devoted to the methods of obtaining the thermosensitive copolymeric hydrogels based on the NIPAAm with acrylic acid and its derivatives such as acrylamide, acrylonitrile, and methylacrylate. The mechanisms of thermoinitiated phase transitions in hydrogel matrices and the regularities of the thermoinitiated release of model compounds and drugs (aniline, novocaine, and sodium diclofenac) from copolymeric hydrogel are investigated.

Knockout reactions: experimental aspects

Energy Technology Data Exchange (ETDEWEB)

Cortina Gil, D. [Santiago de Compostela Univ. (Spain)

2007-07-01

The availability of radioactive beams has given rise to intense activity in the field of direct reactions. The removal of one(two)-nucleon (referred to as nucleon knockout in this text) from a fast exotic projectile has been extensively investigated. This lecture provides a general overview of the experimental results achieved using this technique. The sensitivity of the method to different experimental aspects is illustrated with a few examples. Special attention is given to the application of nucleon-knockout reactions as a general purpose spectroscopic tool. (author)

Knockout reactions: experimental aspects

International Nuclear Information System (INIS)

Cortina Gil, D.

2007-01-01

The availability of radioactive beams has given rise to intense activity in the field of direct reactions. The removal of one(two)-nucleon (referred to as nucleon knockout in this text) from a fast exotic projectile has been extensively investigated. This lecture provides a general overview of the experimental results achieved using this technique. The sensitivity of the method to different experimental aspects is illustrated with a few examples. Special attention is given to the application of nucleon-knockout reactions as a general purpose spectroscopic tool. (author)

Synthesis of copolymerized porous organic frameworks with high gas storage capabilities at both high and low pressures

KAUST Repository

Pei, Cuiying

2014-01-01

A series of copolymerized porous organic frameworks (C-POFs) were synthesized with monomers of tetrakis(4-bromophenyl)methane and tris(4-bromophenyl)amine in different ratios by a Yamamoto-type Ullmann cross-coupling reaction. These C-POFs exhibit high physicochemical stability, large surface areas and excellent H2, CH4 and CO 2 adsorption properties both at low and high pressures. This journal is © the Partner Organisations 2014.

Study on radiation grafting reaction of MMA onto hydroxyapatite

International Nuclear Information System (INIS)

Jiang Bo

1996-01-01

The grafting reaction of MMA onto hydroxyapatite has been studied with the pre-irradiation method in air. The effects of radiation dose, monomer concentration, reaction temperature and inorganic acid on the system are observed. The grafting copolymerization is found to be controlled by the kinetics. If proper kinetic conditions are selected, a better grafting yield can be obtained. Employing weight method, burning method as well as SeM and IR analysis, it has been proved that MMA is definitely grafted onto hydroxyapatite by chemical bonds, which shows that it is possible to improve the interface of inorganic-organic composite materials and to make bioactive ceramics by using radiation induced-grafting copolymerization

Radiation-initiated emulsion copolymerization of styrene and carboxylic acid monomers

International Nuclear Information System (INIS)

Egusa, S.; Makuuchi, K.

1982-01-01

The emulsion copolymerization of styrene and carboxylic acid monomers such as acrylic, methacrylic, and itaconic acids (AAc, MAAc, IAc) was studied by using 60 Co γ-rays as initiator and sodium dodecylsulfate as emulsifier. The polymerization behavior of these acid monomers was followed by simultaneous conductometric and potentiometric titrations for a latex sample taken in polymerization. The polymerization rate of these acid monomers increases in the following order of hydrophobicity: IAc < AAc < MAAc; this suggests that their polymerization sites are mainly the surface and/or subsurface regions of latex particles. The copolymerization rate of styrene and acid monomer increases with an increase in the acid monomer content for AAc and MAAc, whereas for IAc the rate decreases. The particle sizes determined by the stopped-flow method reveal that this variation of copolymerization rate cannot be explained by the number of growing particles and should be attributed to another factor; for instance, the transfer rate of styrene molecules from oil droplets to growing particles

Radiation induced graft copolymerization of jute fibre

International Nuclear Information System (INIS)

Al-Siddique, F.R.; Khan, A.U.; Sheikh, R.A.

1983-01-01

Graft copolymerized jute fibres (GCJF) were prepared by γ-ray induced graft copolymerization of various monomers onto bleached and de-waxed jute samples. The effect of γ-ray dose on the tendency of various monomers to form graft co-polymer was studied. It was found that the tendency decreases as follows: methylmethacrylate (MMA)>acrylonitrile (AN)>styrene (STY)>vinylacetate (VA). When the effect of monomer concentration on the formation of graft co-polymer was studied, it was found that a mixture of AN and STY gave a higher amount of grafting than what was observed for STY or AN alone, when used at a comparable concentration. A study on the effect of concentration of methyl alcohol (a swelling agent for jute) on the tendency of the monomers to form graft co-polymer showed that although there is no effect when only AN is used, an appreciable effect is observed if AN is mixed with STY. In the later case the tendency of graft co-polymerization increases with the increase of CH 3 OH concentration. It was further observed that the increase of CH 3 OH also has a positive influence on MMA to form graft co-polymer in the range of 40-90% CH 3 OH. The affinity of GCJF towards moisture has been found to decrease with the increase of polymer loading onto jute. The presence of swelling agents during graft copolymer formation was also found to decrease the affinity of GCJF towards moisture. (author)

Precise synthesis of thermoreversible block copolymers containing reactive furfuryl groups via living anionic polymerization: the countercation effect on block copolymerization behavior

Energy Technology Data Exchange (ETDEWEB)

Kang, Beom-Goo [ORNL; Pramanik, Nabendu [Indian Institute of Technology, Kharagpur; Singha, Nikhil K [ORNL; Lee, Jae-Suk [ORNL; Mays, Jimmy [University of Tennessee, Knoxville (UTK)

2015-08-07

The anionic block copolymerization of 4,4' -vinylphenyl-N,N-bis(4-tert-butylphenyl)benzenamine (A) with furfuryl isocyanate (B) was carried out using potassium naphthalenide (K-Naph) in tetrahydrofuran at -78 and -98 °C to prepare well-defined block copolymers containing furan groups for the formation of thermoreversible networks via a Diels Alder (DA) reaction. While no block copolymerization was observed in the absence of sodium tetraphenylborate (NaBPh₄) due to side reactions, well-defined poly-(B-b-A-b-B) (PBAB) copolymers with controlled molecular weights (M_n = 18 700 19 500 g mol ^-1) and narrow molecular weight distributions (M_w/M_n = 1.08 -1.17) were successfully synthesized in the presence of excess NaBPh₄. We prevented the occurrence of the undesirable side reactions during polymerization of B of NaBPh₄, which results in the change in the countercation from K⁺ to Na⁺ for further polymerization of B. Moreover, the cross-linking via the DA reaction between the furan groups of PBAB and bismaleimide was proved by FT-IR and differential scanning calorimetry (DSC), and the thermoreversible properties of the cross-linked polymer were subsequently investigated using DSC and solubility testing.

Electronically Stabilized Copoly(Styrene-Acrylic Acid Submicrocapsules Prepared by Miniemulsion Copolymerization

Directory of Open Access Journals (Sweden)

Minkwan Kim

2017-07-01

Full Text Available This work reports the preparation and characterization of poly(styrene-acrylic acid (St/AA submicrocapsules by using the miniemulsion copolymerization method. AA was introduced to miniemulsion polymerization of St to increase the zeta potential and the resulting electrostatic stability of St/AA submicrocapsules. Phytoncide oil was adopted as the core model material. Miniemulsion copolymerization of St and AA was conducted at a fixed monomer concentration (0.172 mol with a varying monomer feed ratio [AA]/[St] (0.2, 0.25, 0.33, 0.5, and 1.0. Concentrations of initiator (azobisisobutyronitrile; 1.0 × 10−3, 2.0 × 10−3, 3.0 × 10−3, and 4.0 × 10−3 mol/mol of monomer and surfactant (sodium dodecyl sulfate; 0.6 × 10−3, 1.0 × 10−3, and 1.4 × 10−3 mol were also controlled to optimize the miniemulsion copolymerization of St and AA. Dynamic light scattering and microscopic analyses confirmed the optimum condition of miniemulsion copolymerization of St and AA. Long-term colloidal stability of aqueous St/AA submicrocapsule suspension was evaluated by using TurbiscanTM Lab. In this work, the optimum condition for miniemulsion copolymerization of St and AA was determined ([AA]/[St] = 0.33; [SDS] = 1.0 × 10−3 mol; [AIBN] = 2.0 × 10−3 mol/mol of monomer. St/AA submicrocapsules prepared at the optimum condition (392.6 nm and −55.2 mV of mean particle size and zeta potential, respectively showed almost no variations in backscattering intensity (stable colloids without aggregation.

Radiation induced copolymerization of N-vinyl-2-pyrrolidone with vinyl acetate [Paper No. RD-3

International Nuclear Information System (INIS)

Ramakrishna, M.S.; Dhal, P.K.; Deshpande, D.D.; Babu, G.N.

1982-01-01

Copolymerization of N-vinyl-2-pyrrolidone (NVP) with vinyl acetate (VAC) was carried out using gamma-ray radiation. The compositions of the copolymers were determined from elemental analysis and the monomer reactivity ratios have been calculated using YBR method. The glass transition temperature and the intrinsic viscosities of the copolymers have been determined. All the experimental results were discussed in terms of the nature of the monomers. (author)

Kinetics and thermodynamics of first-order Markov chain copolymerization

Energy Technology Data Exchange (ETDEWEB)

Gaspard, P.; Andrieux, D. [Center for Nonlinear Phenomena and Complex Systems, Université Libre de Bruxelles, Code Postal 231, Campus Plaine, B-1050 Brussels (Belgium)

2014-07-28

We report a theoretical study of stochastic processes modeling the growth of first-order Markov copolymers, as well as the reversed reaction of depolymerization. These processes are ruled by kinetic equations describing both the attachment and detachment of monomers. Exact solutions are obtained for these kinetic equations in the steady regimes of multicomponent copolymerization and depolymerization. Thermodynamic equilibrium is identified as the state at which the growth velocity is vanishing on average and where detailed balance is satisfied. Away from equilibrium, the analytical expression of the thermodynamic entropy production is deduced in terms of the Shannon disorder per monomer in the copolymer sequence. The Mayo-Lewis equation is recovered in the fully irreversible growth regime. The theory also applies to Bernoullian chains in the case where the attachment and detachment rates only depend on the reacting monomer.

Radiation-induced copolymerization of methyl trifluoroacrylate with α-olefins

International Nuclear Information System (INIS)

Matsuda, O.; Watanabe, T.; Tabata, Y.; Machi, S.

1978-01-01

Paper describes the radiation-induced bulk copolymerization of methyl trifluoroacrylate with various α olefins; propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and isobutylene. MTFA (purity above 98%) was synthesized by method described in literature. Reagent grade α-olefins were used. An equimolar mixture of MTFA and α-olefin was charged into the reactor. Trace amounts of oxygen were purged by the freeze-thaw technique. Irradiation was carried out with gamma rays from a 60 Co source under vapor pressure of the monomers at 25 0 C. The product was precipitated and washed with methanol to remove unreacted monomers, and dried under vacuum at 60 0 C. Infrared spectra of the copolymers were measured; compositions were determined from elemental analysis. Reactivity of the α-olefins appears to be related to the electron density at the double bond. All copolymers were found to have almost equimolar compositions and were soluble in polar solvents such as tetrahydrofuran and acetone. Copolymerization was inhibited completely by the addition of 1,1-diphenyl-2-picrihydrazil, but not by water, indicating that the copolymerization proceeds via a radical mechanism. 1 table; 2 figures

Graft copolymerization of styrene onto poly(vinyl alcohol) initiated by potassium diperiodatocuprate (III)

International Nuclear Information System (INIS)

Bai, L.; Wang, Ch.; Jin, J.; Liu, Y.

2009-01-01

The graft copolymerization of styrene onto poly(vinyl alcohol) is studied by using a novel redox system of potassium diperiodatocuprate-poly(vinyl alcohol) (Cu(III)poly(vinyl alcohol) in alkaline medium. Cu(III)-poly(vinyl alcohol) redox pair is an efficient initiator for this graft copolymerization which is proved by high graft efficiency (>97%) and high percentage of graft (>300%). Reaction conditions (monomer-to-poly(vinyl alcohol) weight ratio, initiator concentration, p H, time and temperature) affect the graft parameters which have been investigated systematically. The optimum reaction conditions are found as St/poly(vinyl alcohol) = 5.4; [Cu(III)] = 1*10 -2 M; p H = 12.7; temperature = 50 d eg C ; time = 3.5 h. Further, the equation of the overall polymerization rate can be written as follows: R p = k C 1.9 (St) C 1.7 (Cu(III)). The overall activation energy was calculated to be 42.0 kJ/mol based on the experimental data of the relations between R p and C(St); R p and C(Cu(III)); and R p and temperature. A mechanism is proposed to explain the formation of radicals and the initiation. The structure of the graft copolymers is confirmed by Fourier transfer infrared spectroscopy. Some peaks were compared with poly(vinyl alcohol) at 3080.34-3001.79 cm -1 (=C-H stretching in the phenyl ring), 1600.34-1450.95 cm -1 (C=C stretching in the phenyl ring), 755.17 cm -1 and 698.64 cm -1 (=C-H out-off-plane bending in phenyl ring) which are considered to belong to the characteristic absorption bands of phenyl group of polystyrene. Therefore it proves that the graft copolymer is composed of poly(vinyl alcohol) and polystyrene. thermal gravimetric analysis thermo grams of poly(vinyl alcohol) and poly(vinyl alcohol)-graft-polystyrene are investigated as well. As it is shown the initial decomposition temperature of poly(vinyl alcohol)-g-polystyrene(377.3 d eg C ) is much higher than that of poly(vinyl alcohol) (241.8 d eg C ), which indicates that the thermal stability of the

Determination of the distribution of graft yields following a radiation-induced graft copolymerization

International Nuclear Information System (INIS)

Schipschack, K.; Wagner, H.; Sawtschenko, L.

1976-01-01

In the radiation-induced graft copolymerization on solid initial polymers a distribution of graft yields takes place along the cross-sections of samples. Methods for determining this distribution, which are described in the literature, are reviewed. In our own investigations boards made of ethylene-vinyl acetate copolymers and grafted with vinyl chloride were used. Distributions of the grafted component obtained by infrared analysis of microtome cuts parallel to the surface are partly rather inhomogeneous, and are interpreted as dependent on the experimental parameters. (author)

Cation-exchanger fabric prepared by electron beam - induced graft copolymerization of binary monomer mixture

International Nuclear Information System (INIS)

Bondar, Yu.V.; Kim, H.J.; Lim, Y.J.; Perelygin, V.P.

2004-01-01

Applying the electron-beam preirradiation method in air the sorption-active polypropylene fiber, containing sulfonic acid (R-SO 3 H) groups, was prepared by simultaneous graft copolymerization of sodium styrenesulfonate with acrylic acid in water solution. The effect of reaction conditions on the grafting yield and reaction mechanism was examined. It was found that the received CEF contains groups of strong acid (R-SO 3 H) and weak acid (R-COOH) in almost equal proportion. The ion-exchange properties of the CEF towards Cu(II) and Co(II) ions were investigated depending on the form of the CEF and a pH of the solution. It was shown that the utilization of the CEF in Na- form allows to make the best use of its ion-exchange capacity. (author)

X-ray structure determination of new monomers to establish their polymerizability: copolymerization of two tetrasubstituted electrophilic olefins with electron-rich styrenes giving polymers with an average 1.25 functional groups per chain carbon atom

International Nuclear Information System (INIS)

Hall, H.K. Jr.; Reineke, K.E.; Ried, J.H.; Sentman, R.C.; Miller, D.

1982-01-01

X-ray crystal structure determination for two tetrasubstituted electrophilic olefins, tetramethyl ethylenetetracarboxylate TMET and dimethyl dicyanofumarate DDCF, revealed two fundamentally different molecular structures. TMET is a nonplanar molecule that possesses two opposite ester groups planar and the others above and below the molecular plane. In contrast, DDCF is a molecule for which both ester groups lie in the plane of the double bond and nitrile groups. DDCF underwent thermal spontaneous copolymerization with electron-rich styrenes to give 1:1 alternating copolymers in moderate yields and molecular weights. These copolymers, which result from the first copolymerization of a tetrasubstituted olefin, possess an average functionality of 1.25 per chain carbon atom. Polymerization is made possible by low steric hindrance and the high delocalization in the propagating radical. The yields were limited by competing cycloaddition reaction. The corresponding diethyl ester also copolymerized, but not so well. Neither electrophilic olefin homopolymerized under γ-irradiation. TMET did not copolymerize at all when treated under identical conditions

Determination of Monomers Reactivity Ratios in Ethyl Acrylate-Methacrylic Acid Copolymerization by Off-Line 1H NMR

Directory of Open Access Journals (Sweden)

Samaneh Ashenagar

2017-03-01

Full Text Available The physical, chemical and mechanical properties of polymer systems depend on the micro-structural characteristics of their macromolecular chains. Along with the most characteristic kinetic parameters in copolymerization reactions are the reactivity ratios, which give a clear idea of the average composition and the monomer sequence distribution in copolymer systems. This research studies the solution radical copolymerization of methacrylic acid (MAA-ethyl acrylate (EA system at low conversion with 2,2'-azobisisobutyronitrile (AIBN as thermal initiator at 60°C in deuterated dimethyl sulfoxide (DMSO-d6 as a reaction solvent. In this case, the monomer reactivity ratios were determined using linear off-line 1H nuclear magnetic resonance spectroscopy (1H NMR methods such as Mayo-Louis, Finemann-Ross, Inverted Finemann-Ross , Ezrielev-Brokhina-Roskin, Joshi-Joshi, Kelen-Tudos, extended Kelen- Tudos, Mao-Huglin at low and high conversions. The next estimation process in off-line 1H NMR methods were performed by applying techniques based on ordinary least square (OLS and generalized least square (GLS. The results showed that the GLS approach compared to the OLS increased regression coefficients (R2 and the order of magnitude of parameter variances obtained from GLS was many times lower than that obtained from OLS. In addition, the monomer reactivity ratios obtained by the Mao-Huglin method and the GLS approach showed the best linear estimation.

Alternating copolymerization of propylene oxide with biorenewable terpene-based cyclic anhydrides: a sustainable route to aliphatic polyesters with high glass transition temperatures.

Science.gov (United States)

Van Zee, Nathan J; Coates, Geoffrey W

2015-02-23

The alternating copolymerization of propylene oxide with terpene-based cyclic anhydrides catalyzed by chromium, cobalt, and aluminum salen complexes is reported. The use of the Diels-Alder adduct of α-terpinene and maleic anhydride as the cyclic anhydride comonomer results in amorphous polyesters that exhibit glass transition temperatures (Tg ) of up to 109 °C. The polymerization conditions and choice of catalyst have a dramatic impact on the molecular weight distribution, the relative stereochemistry of the diester units along the polymer chain, and ultimately the Tg of the resulting polymer. The aluminum salen complex exhibits exceptional selectivity for copolymerization without transesterification or epimerization side reactions. The resulting polyesters are highly alternating and have high molecular weights and narrow polydispersities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bis(formylphenolatocobalt(II-Mediated Alternating Radical Copolymerization of tert-Butyl 2-Trifluoromethylacrylate with Vinyl Acetate

Directory of Open Access Journals (Sweden)

Sanjib Banerjee

2017-12-01

Full Text Available The organometallic-mediated radical polymerization (OMRP of vinyl acetate (VAc and its OMR copolymerization (OMRcoP with tert-butyl 2-trifluoromethylacrylate (MAF-TBE mediated by Co(SAL2 (SAL = 2-formylphenolato or deprotonated salicylaldehyde produced relatively well-defined PVAc and poly(VAc-alt-MAF-TBE copolymers at moderate temperature (<40 °C in bulk. The resulting alternating copolymer was characterized by 1H-, 13C- and 19F-nuclear magnetic resonance (NMR spectroscopies, and by size exclusion chromatography. The linear first-order kinetic plot, the linear evolutions of the molar mass with total monomer conversion, and the relatively low dispersity (Đ~1.55 of the resulting copolymers suggest that this cobalt complex provides some degree of control over the copolymerization of VAc and MAF-TBE. Compared to the previously investigated cobalt complex OMRP mediators having a fully oxygen-based first coordination sphere, this study emphasizes a few peculiarities of Co(SAL2: a lower ability to trap radical chains as compared to Co(acac2 and the absence of catalytic chain transfer reactions, which dominates polymerizations carried in the presence of 9-oxyphenalenone cobalt derivative.

Logarithmic Exchange Kinetics in Monodisperse Copolymeric Micelles

Science.gov (United States)

García Daza, Fabián A.; Bonet Avalos, Josep; Mackie, Allan D.

2017-06-01

Experimental measurements of the relaxation kinetics of copolymeric surfactant exchange for micellar systems unexpectedly show a peculiar logarithmic decay. Several authors use polydispersity as an explanation for this behavior. However, in coarse-grained simulations that preserve microscopic details of the surfactants, we find evidence of the same logarithmic behavior. Since we use a strictly monodisperse distribution of chain lengths such a relaxation process cannot be attributed to polydispersity, but has to be caused by an inherent physical process characteristic of this type of system. This is supported by the fact that the decay is specifically logarithmic and not a power law with an exponent inherited from the particular polydispersity distribution of the sample. We suggest that the degeneracy of the energy states of the hydrophobic block in the core, which is broken on leaving the micelle, can qualitatively explain the broad distribution of energy barriers, which gives rise to the observed nonexponential relaxation.

TUNG OIL BASED MONOMER FOR THERMOSETTING POLYMERS: SYNTHESIS, CHARACTERIZATION AND COPOLYMERIZATION WITH STYRENE

Directory of Open Access Journals (Sweden)

Chengguo Liu,

2011-11-01

Full Text Available A tung oil (TO based monomer for rigid thermosetting polymer was synthesized, characterized, and copolymerized with styrene in this study. Tung oil was alcoholyzed with pentaerythritol (PER to get tung oil pentaerythritol alcoholysis products (TOPER, and the optimized conditions were explored according to the yields of TOPER analyzed by gas chromatography-mass spectrometry (GC-MS. The resulting alcoholysis products were maleinated to form tung oil maleate half ester (TOPERMA, and the reaction conditions were determined by monitoring the reaction extents of TOPER and maleic anhydride (MA with 1HNMR spectroscopy. The TO alcoholysis and maleinization reaction products were characterized by IR, 1HNMR, and electrospray ionization-mass spectrometry (ESI-MS techniques. At last, the TOPERMA mixture was cured with styrene (St, and the initiator tert-butyl peroxy benzoate (TPB. Differential scanning calorimetry (DSC was employed to characterize the curing process. Mechanical properties of the cured TOPERMA/St resin further confirmed the best procedure for the maleinization reaction. The loading of TO reached about 30% weight of the resulting thermosetting polymer. This promising material from renewable resources can be a potential substitution for petroleum products when used as sheet molding compounds.

Constrained Geometry Organotitanium Catalysts Supported on Nanosized Silica for Ethylene (co)Polymerization.

Science.gov (United States)

Li, Kuo-Tseng; Wu, Ling-Huey

2017-05-05

Supported olefin polymerization catalysts can prevent reactor-fouling problems and produce uniform polymer particles. Constrained geometry complexes (CGCs) have less sterically hindered active sites than bis-cyclopentadienyl metallocene catalysts. In the literature, micrometer-sized silica particles were used for supporting CGC catalysts, which might have strong mass transfer limitations. This study aims to improve the activity of supported CGC catalysts by using nanometer-sized silica. Ti[(C₅Me₄)SiMe₂(N t Bu)]Cl₂, a "constrained-geometry" titanium catalyst, was supported on MAO-treated silicas (nano-sized and micro-sized) by an impregnation method. Ethylene homo-polymerization and co-polymerization with 1-octene were carried out in a temperature range of 80-120 °C using toluene as the solvent. Catalysts prepared and polymers produced were characterized. For both catalysts and for both reactions, the maximum activities occurred at 100 °C, which is significantly higher than that (60 °C) reported before for supported bis-cyclopentadienyl metallocene catalysts containing zirconium, and is lower than that (≥140 °C) used for unsupported Ti[(C₅Me₄)SiMe₂(N t Bu)]Me₂ catalyst. Activities of nano-sized catalyst were 2.6 and 1.6 times those of micro-sized catalyst for homopolymerization and copolymerization, respectively. The former produced polymers with higher crystallinity and melting point than the latter. In addition, copolymer produced with nanosized catalyst contained more 1-octene than that produced with microsized catalyst.

Modification of flax fibres by radiation induced emulsion graft copolymerization of glycidyl methacrylate

Science.gov (United States)

Moawia, Rihab Musaad; Nasef, Mohamed Mahmoud; Mohamed, Nor Hasimah; Ripin, Adnan

2016-05-01

Flax fibres were modified by radiation induced graft copolymerization of glycidyl methacrylate (GMA) by pre-irradiation method in an emulsion medium. The effect of reaction parameters on the degree of grafting (DOG) such as concentration of bleaching agent, absorbed dose, monomer concentration, temperature and reaction time were investigated. The DOG was found to be dependent on the investigated parameters. The incorporation of poly(GMA) grafts in the bleached flax fibres was confirmed by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The structural and mechanical changes were evaluated by X-ray diffraction (XRD) and mechanical tester, respectively. The results revealed that reacting bleached flax fibres irradiated with 20 kGy with 5% GMA emulsion containing 0.5% polyoxyethylene-sorbitan monolaurate (Tween 20) surfactant at 40 °C for 1 h led to a maximum DOG of 148%. The grafted fibres showed sufficient mechanical strength and hydrophobicity which make them promising precursors for development of adsorbents after appropriate chemical treatments.

Formation of hyperbranched polymers in atom transfer radical copolymerization of MMA and DVB

Institute of Scientific and Technical Information of China (English)

无

2010-01-01

Hyperbranched poly(methyl methacrylate)s (HPMMAs) have been successfully prepared by atom transfer radical copolymerization of MMA and divinylbenzene (DVB).Kinetic study shows complete consumption of the initiator in 0.5 h,and relatively low polymerization rate when DVB content in the feed was high.By analyzing MALDI-TOF spectra of the resulting copolymers,the linear A n B (n=0,1,2,3) oligomers were formed in 0.5 h of polymerization,and then the oligomers reacted each other to form dimers,further reactions produced HPMMA.The SEC and NMR spectroscopies were used to trace the polymerization,and the results demonstrate that small amount of the branching reactions occur in the initial polymerization,and the branched polymers are significantly generated past a certain conversion depending upon the feed ratios.Raising the content of DVB in the monomer mixture can increase the pendent vinyl groups of the linear oligo-inimers,leading to gelation at low MMA conversion.

Optimization of process parameter for graft copolymerization of glycidyl methacrylate onto delignified banana fibers

International Nuclear Information System (INIS)

Selambakkannu, S.; Nor Azillah Fatimah Othman; Siti Fatahiyah Mohamad

2016-01-01

This paper focused on pre-treated banana fibers as a trunk polymer for optimization of radiation-induced graft copolymerization process parameters. Pre-treated banana fiber was grafted with glycidyl methacrylate (GMA) via electron beam irradiation. Optimization of grafting parameters in term of grafting yield was analyzed at numerous radiation dose, monomer concentration and reaction time. Grafting yield had been calculated gravimetrically against all the process parameters. The grafting yield at 40 kGy had increases from 14 % to 22.5 % at 1 h and 24 h of reaction time respectively. Grafting yield at 1 % of GMA was about 58 % and it increases to 187 % at 3 % GMA. The grafting of GMA onto pre-treated banana fibers confirmed with the characterization using FTIR, SEM and TGA. Grafting of GMA onto pre-treated fibers was successfully carried out and it was confirmed by the results obtained via the characterization. (author)

Radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene in flow system, 7

International Nuclear Information System (INIS)

Watanabe, Hiromasa; Machi, Sueo; Okamoto, Jiro.

1982-02-01

In order to avoid the effects of number of polymer particles on polymerization and bubbles generated by mixing of gaseous monomer and emulsifier-water solution at the early stage of emulsion polymerization, seeded copolymerization of tetrafluoroethylene with propylene by radiation was studied in flow apparatus equipped with tank and pipe type reactors under a pressure of 30 kg/cm 2 and a temperature of 40 0 C. The polymerization rate increases with dose rate and its dose rate exponent changes from 1.0 to 0.5 with increase of dose rate from 10 5 to 10 6 rad/h. In the series of investigation, it was found that the polymer concentration in latex tended to increase accelerately with reaction time. The effects of mean residence time of latex in the reactor and recycle rate of gaseous monomer on the polymerization could not be elucidated because of the acceleration of polymer concentration in latex. The acceleration is assumed to be due to repression of termination reaction by decreases of propylene concentration and mobility of polymer radical in particles with proceeding the polymerization. (author)

Radiation-induced graft copolymerization of methyl acrylate and acrylic acid onto rubber wood fiber

International Nuclear Information System (INIS)

Saliza Jam; Mansor Ahmad; Wan Md Zin Wan Yunus; Khairul Zaman Mohd Dahlan

2001-01-01

Graft copolymerization of methyl acrylate and acrylic acid monomers onto rubber wood fiber (RWF) was carried out by simultaneous radiation-induced technique. The parameters affecting the grafting reaction were investigated and the optimum conditions for both monomers obtained are as follows: impregnation time = 16 hours, total dose = 30 kGy, methanol : water ratio, 3:1, monomers concentration = 40 v/v % and sulphuric acid concentration = 0.1 mol/L. Fourier Transform Infrared (FTIR), thermogravimetry analysis (TGA), and scanning electron microscope (SEM) analyses used to characterize graft copolymers. The structural investigation by x-ray diffraction (XRD) shows the degree of crystallinity of rubber wood fiber decreased with the incorporation of poly(methyl acrylate) and poly(acrylic acid) grafts. (Author)

Alternating copolymerization of fluoroalkenes with carbon monoxide.

Science.gov (United States)

Fujita, Tomoyuki; Nakano, Koji; Yamashita, Makoto; Nozaki, Kyoko

2006-02-15

The palladium-catalyzed alternating copolymerization of fluoroalkenes, represented as CH(2)=CH-CH(2)-C(n)F(2n+1), with CO was performed using (R,S)-BINAPHOS (2e) as a ligand. The CH(2)-C(n)F(2n+1) group is the most electronegative substituent ever reported for the copolymerization (Taft's sigma value of 0.90 for CH(2)CF(3)). The copolymer obtained from CH(2)=CH-CH(2)-C(8)F(17) (1a) existed as a mixture of polyspiroketal and polyketone, while that from CH(2)=CH-CH(2)-C(4)F(9) (1b) was a pure polyspiroketal, as was revealed by infrared and (13)C-CP/MAS NMR spectroscopies. The terminal structure of the polymer from 1b was confirmed by MALDI-TOF MS spectrometry. Detailed NMR studies suggested that the much higher reactivity with (R,S)-BINAPHOS (2e) than that with the conventional ligand DPPP (2a) can be attributed to the unique 1,2-insertion of the fluoroalkene into acylpalladium species. The existence of an electronegative substituent on the alpha-carbon of the palladium center is successfully avoided in the 1,2-insertion mechanism.

In situ NMR and modeling studies of nitroxide mediated copolymerization of styrene and n-butyl acrylate

NARCIS (Netherlands)

Hlalele, L.; Klumperman, L.

2011-01-01

The combination of in situ1H NMR and in situ31P NMR was used to study the nitroxide mediated copolymerization of styrene and n-butyl acrylate. The alkoxyamine MAMA-DEPN was employed to initiate and mediate the copolymerization. The nature of the ultimate/terminal monomer units of dormant polymer

Alternating copolymerization of epoxides with anhydrides initiated by organic bases

Czech Academy of Sciences Publication Activity Database

Hošťálek, Z.; Trhlíková, Olga; Walterová, Zuzana; Martinez, T.; Peruch, F.; Cramail, H.; Merna, J.

2017-01-01

Roč. 88, March (2017), s. 433-447 ISSN 0014-3057 Institutional support: RVO:61389013 Keywords : copolymerization * epoxides * anhydrides Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 3.531, year: 2016

Theoretical analysis of factors controlling the nonalternating CO/C(2)H(4) copolymerization.

Science.gov (United States)

Haras, Alicja; Michalak, Artur; Rieger, Bernhard; Ziegler, Tom

2005-06-22

A [P-O]Pd catalyst based on o-alkoxy derivatives of diphenylphosphinobenzene sulfonic acid (I) has recently been shown by Drent et al. to perform nonalternating CO/C(2)H(4) copolymerization with subsequent incorporation of ethylene units into the polyketone chain. The origin of the nonalternation is investigated in a theoretical study of I, where calculated activation barriers and reaction heats of all involved elementary steps are used to generate a complete kinetic model. The kinetic model is able to account for the observed productivity and degree of nonalternation as a function of temperature. Consistent with the energy changes obtained for the real catalyst model, the selectivity toward a nonalternating distribution of both comonomers appears to be mainly a result of a strong destabilization of the Pd-acyl complex.

The radiation-induced copolymerization of vinyl acetate with dibutyl maleate

International Nuclear Information System (INIS)

Du Plessis, T.A.; Lustig, A.

1975-01-01

The radiation-induced copolymerization of vinyl acetate with dibutyl maleate was investigated in the temperature range from -50 0 to 90 0 . A copolymer of the unsaturated ester with vinyl acetate was obtained in which the comonomers alternate with regularity along the polymer chain over the entire range of comonomer compositions and temperature range investigated. Both the rate of copolymerization and the molecular weight of the resulting copolymer were found to depend strongly on the comonomer composition. The monomer reactivity ratios were found to be practically zero. The apparent activation energy was found to change at 5 0 with an increase in temperature from a value of 1,6 kcal/mole to a value of 4,4kcal/mole. Scavenger studies indicate that a free radical mechanism prevails over the entire temperature range investigated. (Author) [af

Ruthenium phosphine complexes as catalysts for alternating co-polymerization of ethylene and CO

International Nuclear Information System (INIS)

Gusev, O.V.; Kal'sin, A.M.; Peganov, T.A.; Petrovskij, P.V.; Belov, G.P.; Novikova, E.V.

2000-01-01

Ruthenium (2) complexes, [Ru(dppe) 2 (OTs) 2 ] and [Ru(PhP(CH 2 CH 2 CH 2 PPh 2 ) 2 )(OTs) 2 ], where dppe (diphenylphosphino)ethane; OTs = tosylate, were synthesized with the yield of 67 and 76%, respectively, and characterized by 31 P NMR. The properties of the above complexes as catalysts of alternating co-polymerization of ethylene and carbon monoxide were studied. A considerable increase in catalytic activity of the complexes was established in the presence of trifluoroacetic acid and 1,4-benzoquinone. These compounds are the first example of ruthenium complexes that catalyse co-polymerization of ethylene and CO [ru

Identifying Understudied Nuclear Reactions by Text-mining the EXFOR Experimental Nuclear Reaction Library

Energy Technology Data Exchange (ETDEWEB)

Hirdt, J.A. [Department of Mathematics and Computer Science, St. Joseph' s College, Patchogue, NY 11772 (United States); Brown, D.A., E-mail: dbrown@bnl.gov [National Nuclear Data Center, Brookhaven National Laboratory, Upton, NY 11973-5000 (United States)

2016-01-15

The EXFOR library contains the largest collection of experimental nuclear reaction data available as well as the data's bibliographic information and experimental details. We text-mined the REACTION and MONITOR fields of the ENTRYs in the EXFOR library in order to identify understudied reactions and quantities. Using the results of the text-mining, we created an undirected graph from the EXFOR datasets with each graph node representing a single reaction and quantity and graph links representing the various types of connections between these reactions and quantities. This graph is an abstract representation of the connections in EXFOR, similar to graphs of social networks, authorship networks, etc. We use various graph theoretical tools to identify important yet understudied reactions and quantities in EXFOR. Although we identified a few cross sections relevant for shielding applications and isotope production, mostly we identified charged particle fluence monitor cross sections. As a side effect of this work, we learn that our abstract graph is typical of other real-world graphs.

Identifying Understudied Nuclear Reactions by Text-mining the EXFOR Experimental Nuclear Reaction Library

International Nuclear Information System (INIS)

Hirdt, J.A.; Brown, D.A.

2016-01-01

The EXFOR library contains the largest collection of experimental nuclear reaction data available as well as the data's bibliographic information and experimental details. We text-mined the REACTION and MONITOR fields of the ENTRYs in the EXFOR library in order to identify understudied reactions and quantities. Using the results of the text-mining, we created an undirected graph from the EXFOR datasets with each graph node representing a single reaction and quantity and graph links representing the various types of connections between these reactions and quantities. This graph is an abstract representation of the connections in EXFOR, similar to graphs of social networks, authorship networks, etc. We use various graph theoretical tools to identify important yet understudied reactions and quantities in EXFOR. Although we identified a few cross sections relevant for shielding applications and isotope production, mostly we identified charged particle fluence monitor cross sections. As a side effect of this work, we learn that our abstract graph is typical of other real-world graphs.

Radiation-chemical copolymerization of oligoalkylene- maleinants of alicyclic structure

International Nuclear Information System (INIS)

Bondarenko, P.A.; Videnina, N.G.; Omel'chenko, S.I.

1982-01-01

Effect of glycol used in synthesis on the properties of oligoalkylenemaleinates and their copolymers is considered. It is shown that oligoesters during copolymerization with sterol have enough high sensitivity to the effect of gamma radiation and electrons of high energy. The copolymers have a good mechanical-and-physical properties at low absorbed doses

STYRENE/STYRENE-DERIVATIVE COPOLYMERIZATION BY PH2Zn-METALLOCENE-MAO SYSTEMS: HOMO- AND COPOLYMERIZATION OF á-METHYLSTYRENE WITH STYRENE

OpenAIRE

RABAGLIATI, FRANCO M; MUÑOZ, HÉCTOR E; MARDONES, GABRIELA V

2010-01-01

The copolymerization of styrene with á-methylstyrene has been tested using combined metallocene-MAO initiator systems with and without diphenylzinc. The metallocenes used were biscyclopentadienyltitanium dichloride, Cp2TiCl2, bis(n-butylcyclopentadienyl)titanium dichloride, (n-BuCp)2TiCl2, and the half-sandwich metallocene indenyltitanium trichloride, IndTiCl3. The results indicate that both binary metallocene-MAO, and ternary Ph2Zn-metallocene-MAO systems are capable of polymerizing á-methyl...

Polytetrafluorethylene (PTFE) copolymerization with N-N'- dimethyl acrylamide (DMAA) using gamma radiation

International Nuclear Information System (INIS)

Queiroz, A.A. de; Higa, O.Z.

1990-01-01

The copolymerization of N-N'-dimethylacrylamide monomer with polytetrafluorethylene was made using an insert technique by gamma irradiation. The polimeric surface was characterized by electron microscopy. (author) [pt

Spectroscopic study of monitoring the kinetics of radical copolymerization of di(ethylene glycol) bis(allylcarbonate) and 2-naphthylmethacrylate

Science.gov (United States)

Barashkov, N. N.; Novikova, T. S.; Sakhno, T. V.; Bulgakova, L. M.

1996-03-01

The results of fluorescence monitoring in the radical copolymerization of di(ethylene glycol) bis(allylcarbonate) and 2-naphthylmethacrylate are discussed. Our studies suggest that data based on measurement of the intensity of the fluorescence band at 345 nm during copolymerization are in good agreement with the data obtained by the traditional dilatometric method.

Salphen-Co(III) complexes catalyzed copolymerization of epoxides with CO2

Czech Academy of Sciences Publication Activity Database

Hošťálek, Z.; Mundil, R.; Císařová, I.; Trhlíková, Olga; Grau, E.; Peruch, F.; Cramail, H.; Merna, J.

2015-01-01

Roč. 63, 20 April (2015), s. 52-61 ISSN 0032-3861 Institutional support: RVO:61389013 Keywords : cobalt salphen catalyst * CO2 epoxide copolymerization * MALDI-TOF Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.586, year: 2015

LPV model development and control of a solution copolymerization reactor

NARCIS (Netherlands)

Rahme, S.; Abbas, H.M.S.; Meskin, N.; Tóth, R.; Mohammadpour, J.

2016-01-01

In this paper, linear parameter-varying (LPV) control is considered for a solution copolymerization reactor, which takes into account the time-varying nature of the parameters of the process. The nonlinear model of the process is first converted to an exact LPV model representation in the

Comparison of Polymer Networks Synthesized by Conventional Free Radical and RAFT Copolymerization Processes in Supercritical Carbon Dioxide

OpenAIRE

Patricia Pérez-Salinas; Gabriel Jaramillo-Soto; Alberto Rosas-Aburto; Humberto Vázquez-Torres; María Josefa Bernad-Bernad; Ángel Licea-Claverie; Eduardo Vivaldo-Lima

2017-01-01

There is a debate in the literature on whether or not polymer networks synthesized by reversible deactivation radical polymerization (RDRP) processes, such as reversible addition-fragmentation radical transfer (RAFT) copolymerization of vinyl/divinyl monomers, are less heterogeneous than those synthesized by conventional free radical copolymerization (FRP). In this contribution, the syntheses by FRP and RAFT of hydrogels based on 2-hydroxyethylene methacrylate (HEMA) and ethylene glycol dimet...

In-situ radiation dosimetry based on Radio-Fluorogenic Co-Polymerization

NARCIS (Netherlands)

Warman, J.M.; Luthjens, L.H.; De Haas, M.P.

2009-01-01

A fluorimetric method of radiation dosimetry is presented for which the intensity of the fluorescence of a (tissue equivalent) medium is linearly dependent on accumulated dose from a few Gray up to kiloGrays. The method is based on radio-fluorogenic co-polymerization (RFCP) in which a normally very

Modification of flax fibres by radiation induced emulsion graft copolymerization of glycidyl methacrylate

International Nuclear Information System (INIS)

Moawia, Rihab Musaad; Nasef, Mohamed Mahmoud; Mohamed, Nor Hasimah; Ripin, Adnan

2016-01-01

Flax fibres were modified by radiation induced graft copolymerization of glycidyl methacrylate (GMA) by pre-irradiation method in an emulsion medium. The effect of reaction parameters on the degree of grafting (DOG) such as concentration of bleaching agent, absorbed dose, monomer concentration, temperature and reaction time were investigated. The DOG was found to be dependent on the investigated parameters. The incorporation of poly(GMA) grafts in the bleached flax fibres was confirmed by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The structural and mechanical changes were evaluated by X-ray diffraction (XRD) and mechanical tester, respectively. The results revealed that reacting bleached flax fibres irradiated with 20 kGy with 5% GMA emulsion containing 0.5% polyoxyethylene-sorbitan monolaurate (Tween 20) surfactant at 40 °C for 1 h led to a maximum DOG of 148%. The grafted fibres showed sufficient mechanical strength and hydrophobicity which make them promising precursors for development of adsorbents after appropriate chemical treatments. - Highlights: • Flax fibers were modified by radiation induced emulsion grafting of GMA. • Bleaching with 0.7 wt% Na-chlorite was essential for achieving high DOGs. • Effect of reaction parameters on the degree of grafting were established. • The incorporation of poly-GMA grafts was proved by SEM, FTIR and XRD. • The obtained poly-GMA grafted flax fibers have potential for adsorbent making.

Surrogate Models for Online Monitoring and Process Troubleshooting of NBR Emulsion Copolymerization

Directory of Open Access Journals (Sweden)

Chandra Mouli R. Madhuranthakam

2016-03-01

Full Text Available Chemical processes with complex reaction mechanisms generally lead to dynamic models which, while beneficial for predicting and capturing the detailed process behavior, are not readily amenable for direct use in online applications related to process operation, optimisation, control, and troubleshooting. Surrogate models can help overcome this problem. In this research article, the first part focuses on obtaining surrogate models for emulsion copolymerization of nitrile butadiene rubber (NBR, which is usually produced in a train of continuous stirred tank reactors. The predictions and/or profiles for several performance characteristics such as conversion, number of polymer particles, copolymer composition, and weight-average molecular weight, obtained using surrogate models are compared with those obtained using the detailed mechanistic model. In the second part of this article, optimal flow profiles based on dynamic optimisation using the surrogate models are obtained for the production of NBR emulsions with the objective of minimising the off-specification product generated during grade transitions.

Radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene in flow system, 8

International Nuclear Information System (INIS)

Watanabe, Hiromasa; Ito, Masayuki; Machi, Sueo; Okamoto, Jiro.

1982-02-01

Seeded copolymerization of tetrafluoroethylene with propylene by radiation was carried out in a flow apparatus with pipe reactor at a pressure of 30 kg/cm 2 , a temperature of 40 0 C, a propylene fraction in monomer gas of 0.1, and at various dose rates. Amounts of dissolved monomer in latex increases in proportion to the polymer concentration, however, it becomes lower than that in equilibrium as polymerization proceeds. Propylene fraction in the dissolved monomer decreases with reaction time. Polymer concentration in latex increases accelerately with reaction time, and polymerization rate increases and tends to level off when the polymer concentration exceeds 100 g/l-H 2 O at higher dose rate. Polymerization rate is proportional to the 0.6 power of the dose rate at the polymer concentration of 50 g/l-H 2 O, and the power factor decreases from 0.46 to 0.39 with increasing the concentration from 100 to 150 g/l-H 2 O. Molecular weight of the polymer is proportional to the -0.17 power of the dose rate. The dose rate effects are explained by considering both first-order termination by degradative chain transfer to propylene and second-order termination by recombination. (author)

Novel star-type methoxy-poly(ethylene glycol) (PEG)-poly({epsilon}-caprolactone) (PCL) copolymeric nanoparticles for controlled release of curcumin

Energy Technology Data Exchange (ETDEWEB)

Feng Runliang; Zhu Wenxia; Song Zhimei, E-mail: zhimei_song@126.com [University of Jinan, Shandong Academy of Medical Science, Department of Pharmaceutical Engineering, School of Medicine and Life Sciences (China); Zhao Liyan [Hebei North University, Department of Pharmacy (China); Zhai Guangxi [Shandong University, Department of Pharmaceutics, College of Pharmacy (China)

2013-06-15

To improve curcumin's (CURs) water solubility and release property, a novel star methoxy poly(ethylene glycol)-poly({epsilon}-caprolactone) (MPEG-PCL) copolymer was synthesized through O-alkylation, basic hydrolysis and ring-opening polymerization reaction with MPEG, epichlorohydrin, and {epsilon}-caprolactone as raw materials. The structure of the novel copolymer was characterized by {sup 1}H NMR, FT-IR, and GPC. The results of FT-IR and differential scanning calorimeter of CUR-loaded nanoparticles (NPs) prepared by dialysis method showed that CUR was successfully encapsulated into the SMP12 copolymeric NPs with 98.2 % of entrapment efficiency, 10.91 % of drug loading, and 88.4 {+-} 11.2 nm of mean particle diameter in amorphous forms. The dissolubility of nanoparticulate CUR was increased by 1.38 Multiplication-Sign 10{sup 5} times over CUR in water. The obtained blank copolymer showed no hemolysis. A sustained CUR release to a total of approximately 56.13 % was discovered from CUR-NPs in 40 % of ethanol saline solution within 72 h on the use of dialysis method. The release behavior fitted the ambiexponent and biphasic kinetics equation. In conclusion, the copolymeric NPs loading CUR might serve as a potential nanocarrier to improve the solubility and release property of CUR.

Novel star-type methoxy-poly(ethylene glycol) (PEG)-poly(ɛ-caprolactone) (PCL) copolymeric nanoparticles for controlled release of curcumin

Science.gov (United States)

Feng, Runliang; Zhu, Wenxia; Song, Zhimei; Zhao, Liyan; Zhai, Guangxi

2013-06-01

To improve curcumin's (CURs) water solubility and release property, a novel star methoxy poly(ethylene glycol)-poly(ɛ-caprolactone) (MPEG-PCL) copolymer was synthesized through O-alkylation, basic hydrolysis and ring-opening polymerization reaction with MPEG, epichlorohydrin, and ɛ-caprolactone as raw materials. The structure of the novel copolymer was characterized by 1H NMR, FT-IR, and GPC. The results of FT-IR and differential scanning calorimeter of CUR-loaded nanoparticles (NPs) prepared by dialysis method showed that CUR was successfully encapsulated into the SMP12 copolymeric NPs with 98.2 % of entrapment efficiency, 10.91 % of drug loading, and 88.4 ± 11.2 nm of mean particle diameter in amorphous forms. The dissolubility of nanoparticulate CUR was increased by 1.38 × 105 times over CUR in water. The obtained blank copolymer showed no hemolysis. A sustained CUR release to a total of approximately 56.13 % was discovered from CUR-NPs in 40 % of ethanol saline solution within 72 h on the use of dialysis method. The release behavior fitted the ambiexponent and biphasic kinetics equation. In conclusion, the copolymeric NPs loading CUR might serve as a potential nanocarrier to improve the solubility and release property of CUR.

Catalytic copolymerization of CO and ethylene with a charge neutral palladium(II) zwitterion.

Science.gov (United States)

Lu, Connie C; Peters, Jonas C

2002-05-15

The synthesis of a zwitterionic Pd(II) complex supported by an anionic bis(phosphino)borate ligand, Ph(2)B(CH(2)PPh(2))(2) (abbreviated as [Ph(2)BP(2)]), is reported. The new complex, [Ph(2)BP(2)]PdMe(THF), is active for CO and ethylene copolymerization. The copolymerization activity and polyketone molecular weight for the neutral, zwitterionic system are compared with those for the cationic systems [R(2)E(CH(2)PPh(2))(2)PdMe(THF)][B(C(6)F(5))(4)] where ER(2) = SiPh(2) and CH(2). Surprisingly, the more electron rich zwitterionic system is a catalyst of activity comparable to that of the more conventional cationic systems.

Optimal Design for Reactivity Ratio Estimation: A Comparison of Techniques for AMPS/Acrylamide and AMPS/Acrylic Acid Copolymerizations

Directory of Open Access Journals (Sweden)

Alison J. Scott

2015-11-01

Full Text Available Water-soluble polymers of acrylamide (AAm and acrylic acid (AAc have significant potential in enhanced oil recovery, as well as in other specialty applications. To improve the shear strength of the polymer, a third comonomer, 2-acrylamido-2-methylpropane sulfonic acid (AMPS, can be added to the pre-polymerization mixture. Copolymerization kinetics of AAm/AAc are well studied, but little is known about the other comonomer pairs (AMPS/AAm and AMPS/AAc. Hence, reactivity ratios for AMPS/AAm and AMPS/AAc copolymerization must be established first. A key aspect in the estimation of reliable reactivity ratios is design of experiments, which minimizes the number of experiments and provides increased information content (resulting in more precise parameter estimates. However, design of experiments is hardly ever used during copolymerization parameter estimation schemes. In the current work, copolymerization experiments for both AMPS/AAm and AMPS/AAc are designed using two optimal techniques (Tidwell-Mortimer and the error-in-variables-model (EVM. From these optimally designed experiments, accurate reactivity ratio estimates are determined for AMPS/AAm (rAMPS = 0.18, rAAm = 0.85 and AMPS/AAc (rAMPS = 0.19, rAAc = 0.86.

Metal-Free Alternating Copolymerization of CO2with Epoxides: Fulfilling “Green” Synthesis and Activity

KAUST Repository

Zhang, Dongyue

2016-08-16

Polycarbonates were successfully synthesized for the first time through the anionic copolymerization of epoxides with CO2, under metal-free conditions. Using an approach based on the activation of epoxides by Lewis acids and of CO, by appropriate cations, well-defined alternating copolymers made of CO, and propylene oxide (PO) or cyclohexene oxide (CHO) were indeed obtained. Triethyl borane was the Lewis acid chosen to activate the epoxides, and onium halides or onium alkoxides involving either ammonium, phosphonium, or phosphazenium cations were selected to initiate the copolymerization. In the case of PO, the carbonate content of the poly(propylene carbonate) formed was in the range of 92-99% and turnover numbers (TON) were close to 500; in the case of CHO perfectly alternating poly(cyclohexene carbonate) were obtained and TON values were close to 4000. The advantages of such a copolymerization system are manifold: (i) no need for multistep catalyst/ligand synthesis as in previous works; (ii) no transition metal involved in the copolymer synthesis and therefore no coloration of the samples isolated; and (iii) no necessity for postsynthesis purification.

Experimental evaluation of improved dual temperature hydrogen isotopic exchange reaction system

International Nuclear Information System (INIS)

Asakura, Yamato; Uchida, Shunsuke

1984-01-01

A proposed dual temperature hydrogen isotopic exchange reaction system between water and hydrogen gas is evaluated experimentally. The proposed system is composed of low temperature co-current reactors for reaction between water mists and hydrogen gas and high temperature co-current reactors for reaction between water vapor and hydrogen gas. Thus, operation is possible under atmospheric pressure with high reaction efficiency. Using the pilot test system which is composed of ten low temperature (30 0 C) reaction units and ten high temperature (200 0 C) reaction units, an experimental separation of deuterium from light water is carried out. The enrichment factor under steady state conditions, its dependency on operating time, and the reaction period necessary to obtain the steady state enrichment factor are determined experimentally and compared with calculations. It is shown that separation ability in a multistage reaction system can be estimated by numerical calculation using actual reaction efficiency in a unit reactor. (author)

Surface modification of poly(tetrafluoroethylene) films by low energy Ar+ ion-beam activation and UV-induced graft copolymerization

International Nuclear Information System (INIS)

Zhang Yan; Huan, A.C.H.; Tan, K.L.; Kang, E.T.

2000-01-01

Surface modification of poly(tetrafluoroethylene) (PTFE) films by Ar + ion-beam irradiation with varying ion energy and ion dose was carried out. The changes in surface composition of the irradiated PTFE films were characterized, both in situ and after exposure to air, by X-ray photoelectron spectroscopy (XPS). The possible mechanisms of chemical reaction induced by the incident ion beam on the surface of PTFE film included defluorination, chain scission and cross-linking, as indicated by the presence of the characteristic peak components associated with the - - -CF 3 , - - -CF, and C(CF 2 ) 4 species in the C 1s core-level spectra, the decrease in surface [F]/[C] ratio, and the increase in surface micro-hardness of the Ar + ion-beam-treated PTFE films. Furthermore, the free radicals generated by the ion-beam could react with oxygen in the air to give rise to oxidized carbon species, such as the peroxides, on the PTFE surface. Thus, after exposure to air, the Ar + ion-beam-pretreated PTFE films were susceptible to further surface modification by UV-induced graft copolymerization with a vinyl monomer, such as acrylamide (AAm). The graft concentrations were deduced from the XPS-derived surface stoichiometries. The Ar + ion energy and the ion dose affected not only the surface composition of the treated films but also the graft copolymerization efficiency of the corresponding pretreated films

Novel star-type methoxy-poly(ethylene glycol) (PEG)–poly(ε-caprolactone) (PCL) copolymeric nanoparticles for controlled release of curcumin

International Nuclear Information System (INIS)

Feng Runliang; Zhu Wenxia; Song Zhimei; Zhao Liyan; Zhai Guangxi

2013-01-01

To improve curcumin’s (CURs) water solubility and release property, a novel star methoxy poly(ethylene glycol)–poly(ε-caprolactone) (MPEG–PCL) copolymer was synthesized through O-alkylation, basic hydrolysis and ring-opening polymerization reaction with MPEG, epichlorohydrin, and ε-caprolactone as raw materials. The structure of the novel copolymer was characterized by 1 H NMR, FT-IR, and GPC. The results of FT-IR and differential scanning calorimeter of CUR-loaded nanoparticles (NPs) prepared by dialysis method showed that CUR was successfully encapsulated into the SMP12 copolymeric NPs with 98.2 % of entrapment efficiency, 10.91 % of drug loading, and 88.4 ± 11.2 nm of mean particle diameter in amorphous forms. The dissolubility of nanoparticulate CUR was increased by 1.38 × 10 5 times over CUR in water. The obtained blank copolymer showed no hemolysis. A sustained CUR release to a total of approximately 56.13 % was discovered from CUR-NPs in 40 % of ethanol saline solution within 72 h on the use of dialysis method. The release behavior fitted the ambiexponent and biphasic kinetics equation. In conclusion, the copolymeric NPs loading CUR might serve as a potential nanocarrier to improve the solubility and release property of CUR.

Experimental and numerical reaction analysis on sodium-water chemical reaction field

International Nuclear Information System (INIS)

Deguchi, Yoshihiro; Takata, Takashi; Yamaguchi, Akira; Kikuchi, Shin; Ohshima, Hiroyuki

2015-01-01

In a sodium-cooled fast reactor (SFR), liquid sodium is used as a heat transfer fluid because of its excellent heat transport capability. On the other hand, it has strong chemical reactivity with water vapor. One of the design basis accidents of the SFR is the water leakage into the liquid sodium flow by a breach of heat transfer tubes. This process ends up damages on the heat transport equipment in the SFR. Therefore, the study on sodium-water chemical reactions is of paramount importance for security reasons. This study aims to clarify the sodium-water reaction mechanisms using an elementary reaction analysis. A quasi one-dimensional flame model is applied to a sodium-water counter-flow reaction field. The analysis contains 25 elementary reactions, which consist of 17 H_2-O_2 and 8 Na-H_2O reactions. Temperature and species concentrations in the counter-flow reaction field were measured using laser diagnostics such as LIF and CARS. The main reaction in the experimental conditions is Na+H_2O → NaOH+H and OH is produced by H_2O+H → H_2+OH. It is demonstrated that the reaction model in this study well explains the structure of the sodium-water counter-flow diffusion flame. (author)

Stable and pH-responsive core-shell nanoparticles based on HEC and PMAA networks via template copolymerization

Science.gov (United States)

Zhang, Y.; Jin, Q.; Chen, Y.; Zhao, J.

2011-10-01

Taking advantage of the specific hydrogen bonding interactions, stable and pH-responsive core-shell nanoparticles based on hydroxyethyl cellulose (HEC) and polymethacrylic acid (PMAA) networks, with a size ranging from 190 to 250 nm, can be efficiently prepared via facile one-step co-polymerization of methacrylic acid (MAA) and N, N'-methylenebisacrylamide (MBA) on HEC template in water. Using dynamic light scattering, electrophoretic light scattering, fluorescence spectrometry, thermo-gravimetric analysis, TEM, and AFM observations, the influence of crosslinker MBA as well as the reaction parameters were studied. The results show that after the introduction of crosslinker MBA, the nanoparticles became less compact; their size exhibited a smaller pH sensitivity, and their stability against pH value was improved greatly. Furthermore, the size, structure, and pH response of the nanoparticles can be adjusted via varying the reaction parameters: nanoparticles of smaller size, more compact structure, and higher swelling capacity were produced as pH value of the reaction medium increased or the HEC/MAA ratio decreased; while nanoparticles of smaller size, less compact structure and smaller swelling capacity were produced as the total feeding concentration increased.

Polyfunctional monomers as additives for enhancing the radiation copolymerization of styrene with polyethylene, polypropylene, and PVC

International Nuclear Information System (INIS)

Ang, C.H.; Garnett, J.L.; Levot, R.; Long, M.A.

1982-01-01

Additives which can increase the yield in the radiation grafting of monomers to polymers are useful. The use of polyfunctional monomers as additives (approx. = 1% v/v) are shown to enhance significantly the copolymerization yields of styrene in methanol to films of polyethylene and polypropylene under certain radiation conditions. The results obtained when the polyolefins are replaced by PVC as backbone polymer in these accelerated grafting reactions are reported. Divinylbenzene (DVB) and trimethylolpropane triacrylate (TMPTA) were used as representative polyfunctional monomers for the enhancement effect. When polypropylene was used as backbone polymer, the inclusion of DVB significantly enhanced the radiation grafting of styrene in methanol at all monomer concentrations studied above 35%. At certain monomer concentrations (50% , 60%), the yield of graft copolymer was almost doubled by the addition of DVB. 3 tables. (DP)

Characterisation of Microbial Cellulose Modified by Graft Copolymerization Technique

International Nuclear Information System (INIS)

Tita Puspitasari; Cynthia Linaya Radiman

2008-01-01

Chemical and phisycal modifications of polymer can be carried out by radiation induced graft copolymerization. This research was carried out to study the morphology and crystallinity of microbial cellulose copolymer grafted by acrylic acid (MC-g-AAC). The SEM microstructural analysis proved that the acrylic acid could diffuse into the microbial celullose and resulted a dense structure. Crystallinity measurement showded that the crystalinity of microbial cellulose increase from 50 % to 53 % after modification. (author)

[Are there pseudophototropic reactions in biology? Part 4: On the reversibility of biologic/synthetic polymere systems (author's transl)].

Science.gov (United States)

Patschorke, J

1979-01-01

In further research on pseudophototropic behaviour in cellular membranes of halobacteria the reversibility of vinylmethylethermaleic anhydride-copolymeres with biological liquids is tested and the basic principles of different colour generating reactions are studied.

Modeling of continuous free-radical butadiene-styrene copolymerization process by the Monte Carlo method

Directory of Open Access Journals (Sweden)

T. A. Mikhailova

2016-01-01

Full Text Available In the paper the algorithm of modeling of continuous low-temperature free-radical butadiene-styrene copolymerization process in emulsion based on the Monte-Carlo method is offered. This process is the cornerstone of industrial production butadiene – styrene synthetic rubber which is the most widespread large-capacity rubber of general purpose. Imitation of growth of each macromolecule of the formed copolymer and tracking of the processes happening to it is the basis of algorithm of modeling. Modeling is carried out taking into account residence-time distribution of particles in system that gives the chance to research the process proceeding in the battery of consistently connected polymerization reactors. At the same time each polymerization reactor represents the continuous stirred tank reactor. Since the process is continuous, it is considered continuous addition of portions to the reaction mixture in the first reactor of battery. The constructed model allows to research molecular-weight and viscous characteristics of the formed copolymerization product, to predict the mass content of butadiene and styrene in copolymer, to carry out calculation of molecular-weight distribution of the received product at any moment of conducting process. According to the results of computational experiments analyzed the influence of mode of the process of the regulator introduced during the maintaining on change of characteristics of the formed butadiene-styrene copolymer. As the considered process takes place with participation of monomers of two types, besides listed the model allows to research compositional heterogeneity of the received product that is to carry out calculation of composite distribution and distribution of macromolecules for the size and structure. On the basis of the proposed algorithm created the software tool that allows you to keep track of changes in the characteristics of the resulting product in the dynamics.

Emprego de catalisadores à base de níquel para homo- e copolimerização de estireno The use of nickel-based catalysts for homo-and copolymerization of styrene

Directory of Open Access Journals (Sweden)

Luis Carlos Ferreira Jr.

2004-12-01

Full Text Available This review deals with the homo- and copolymerization of styrene with nickel catalysts. The catalytic activity, polymer stereoregularity, polymer molecular weight and polydispersity are dependent upon nickel ligands and reaction parameters. Catalysts supported on silica, treated with methylaluminoxane (MAO, have shown higher stereospecificity and activity compared to homogeneous ones. The influence of these parameters is discussed focusing on the elucidation of some aspects of the polymerization mechanism.

Influence Of Initiator Types And Emulsion Polymerization Techniques To Particle Size Of Copolymerization Styrene-Butyl Acrylate-Methyl Methacrylate

Directory of Open Access Journals (Sweden)

Ariyanti Sarwono

2008-11-01

Full Text Available Influence of initiator types and emulsion polymerization techniques to particle size of copolymerization styrene-butyl acrylate-methyl methacrylate. Copoly(styrene/butyl acrylic/methyl methacrylic was prepared by emulsion polymerization method. This paper describes effect of insiator types i.e. ammonium persulfate (APS, hydrogen peroxide, ters-butyl peroxide (TBHP, initiator redox (H2O2/ascorbic acid and polymerization techniques i.e. batch and semicontinue to particle size distribution of copoly(styrene/butyl acrylic/methyl methacrylic. Initiator TBHP and H2O2 could not initiate copolymerization properly, but initiator APS and redox initiate copolymerization with batch and semi continue techniques could well perform. The higher concentration of APS, the greater particle size of the copolymer, but the copolymer is polymodal. Initiator redox (H2O2/ascorbic acid produced greater particle size than initiator redox (ascorbic acid/ H2O2.

Synthesis, Cyclopolymerization and Cyclo-Copolymerization of 9-(2-Diallylaminoethyladenine and Its Hydrochloride Salt

Directory of Open Access Journals (Sweden)

Karyn Usher

2012-11-01

Full Text Available We report herein the synthesis and characterization of 9-(2-diallylaminoethyl adenine. We evaluated two different synthetic routes starting with adenine where the optimal route was achieved through coupling of 9-(2-chloroethyladenine with diallylamine. The cyclopolymerization and cyclo-copolymerization of 9-(2-diallylaminoethyladenine hydrochloride salt resulted in low molecular weight oligomers in low yields. In contrast, 9-(2-diallylaminoethyladenine failed to cyclopolymerize, however, it formed a copolymer with SO2 in relatively good yields. The molecular weights of the cyclopolymers were around 1,700–6,000 g/mol, as estimated by SEC. The cyclo-copolymer was stable up to 226 °C. To the best of our knowledge, this is the first example of a free-radical cyclo-copolymerization of a neutral alkyldiallylamine derivative with SO2. These polymers represent a novel class of carbocyclic polynucleotides.

Swelling and drug release behavior of poly(2-hydroxyethyl methacrylate/itaconic acid) copolymeric hydrogels obtained by gamma irradiation

International Nuclear Information System (INIS)

Tomic, S.Lj.; Micic, M.M.; Filipovic, J.M.; Suljovrujic, E.H.

2007-01-01

The new copolymeric hydrogels based on 2-hydroxyethyl methacrylate (HEMA) and itaconic acid (IA) were prepared by gamma irradiation, in order to examine the potential use of these hydrogels in controlled drug release systems. The influence of IA content in the gel on the swelling characteristics and the releasing behavior of hydrogels, and the effect of different drugs, theophylline (TPH) and fenethylline hydrochloride (FE), on the releasing behavior of P(HEMA/IA) matrix were investigated in vitro. The diffusion exponents for swelling and drug release indicate that the mechanisms of buffer uptake and drug release are governed by Fickian diffusion. The swelling kinetics and, therefore, the release rate depends on the matrix swelling degree. The drug release was faster for copolymeric hydrogels with a higher content of itaconic acid. Furthermore, the drug release for TPH as model drug was faster due to a smaller molecular size and a weaker interaction of the TPH molecules with(in) the P(HEMA/IA) copolymeric networks

Reaction of CO2 with propylene oxide and styrene oxide catalyzed by a chromium(III) amine-bis(phenolate) complex.

Science.gov (United States)

Dean, Rebecca K; Devaine-Pressing, Katalin; Dawe, Louise N; Kozak, Christopher M

2013-07-07

A diamine-bis(phenolate) chromium(III) complex, {CrCl[O2NN'](BuBu)}2 catalyzes the copolymerization of propylene oxide with carbon dioxide. The synthesis of this metal complex is straightforward and it can be obtained in high yields. This catalyst incorporates a tripodal amine-bis(phenolate) ligand, which differs from the salen or salan ligands typically used with Cr and Co complexes that have been employed as catalysts for the synthesis of such polycarbonates. The catalyst reported herein yields low molecular weight polymers with narrow polydispersities when the reaction is performed at room temperature. Performing the reaction at elevated temperatures causes the selective synthesis of propylene carbonate. The copolymerization activity for propylene oxide and carbon dioxide, as well as the coupling of carbon dioxide and styrene oxide to give styrene carbonate are presented.

Selective Release of anti–TB Drugs Complex from Smart Copolymeric Bioactive nano–carriers

Directory of Open Access Journals (Sweden)

Alejandro Arredondo–Peñaranda

2014-07-01

Full Text Available Smart nano–copolymeric matrices have been employed to load and release anti tuberculosis (anti – TB drugs combinated complexes of Ethambutol (EMB, Isoniazid (INH, Rifampicin (RMP and Pyrazinamide (PZA. Copolymeric nanocarriers were synthesized using a microemulsion polymerization method previously reported. These nanocarriers can show selective swelling–collapse response under changes in local environments such a temperature, pH, solvent composition and electrical stimuli. The employ of these kinds of systems permits a controlled and selective delivery and release on specific human tissues. High Performance Liquid Chromatography technique was used to allow the detection of combinated mixtures of different active principles of anti–TB drugs using an acetonitrile mobile phase at 0.5 mL/min of flow rate whit a Spherisorb ODS2, C18 column. The results obtained suggest that the employ of smart nanohydrogels is a novel method in several tuberculosis therapies.

Experimental and Theoretical Investigation of Shock-Induced Reactions in Energetic Materials

Energy Technology Data Exchange (ETDEWEB)

Kay, Jeffrey J. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Park, Samuel [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Kohl, Ian Thomas [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Knepper, Robert [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Farrow, Darcie [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Tappan, Alexander S. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2017-09-01

In this work, shock-induced reactions in high explosives and their chemical mechanisms were investigated using state-of-the-art experimental and theoretical techniques. Experimentally, ultrafast shock interrogation (USI, an ultrafast interferometry technique) and ultrafast absorption spectroscopy were used to interrogate shock compression and initiation of reaction on the picosecond timescale. The experiments yielded important new data that appear to indicate reaction of high explosives on the timescale of tens of picoseconds in response to shock compression, potentially setting new upper limits on the timescale of reaction. Theoretically, chemical mechanisms of shock-induced reactions were investigated using density functional theory. The calculations generated important insights regarding the ability of several hypothesized mechanisms to account for shock-induced reactions in explosive materials. The results of this work constitute significant advances in our understanding of the fundamental chemical reaction mechanisms that control explosive sensitivity and initiation of detonation.

Status of experimental data for neutron induced reactions

Energy Technology Data Exchange (ETDEWEB)

Baba, Mamoru [Tohoku Univ., Sendai (Japan)

1998-11-01

A short review is presented on the status of experimental data for neutron induced reactions above 20 MeV based on the EXFOR data base and journals. Experimental data which were obtained in a systematic manner and/or by plural authors are surveyed and tabulated for the nuclear data evaluation and the benchmark test of the evaluated data. (author). 61 refs.

Catalytic Copolymerization of Ethene and Carbon Monoxide on Nickel Complexes.

Science.gov (United States)

Domhöver, Bernd; Kläui, Wolfgang; Kremer-Aach, Andreas; Bell, Ralf; Mootz, Dietrich

1998-11-16

Can palladium be replaced by nickel? For the industrial copolymerization of carbon monoxide and ethene a palladium catalyst is used which cannot be recovered-a cheaper procedure would be desirable. The presented complex 1 is the first structurally characterized nickel compound which does not polymerize ethene but a mixture from carbon monoxide and ethene unter mild conditions to give a perfectly alternating polyketone. © 1998 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

Radiation induced graft copolymerization for preparation of cation exchange membranes: a review

International Nuclear Information System (INIS)

Mohamed Mahmoud Nasef; Hamdani Saidi; Hussin Mohd Nor

1999-01-01

Cation exchange membranes are regarded as the ideal solid polymer electrolyte materials for the development of various electrochemical energy conversion applications where significant improvements in the current density are required. Such membranes require special polymers and preparation techniques to maintain high chemical , mechanical and thermal stability in addition to high ionic conductivity and low resistance. A lot of different techniques have been proposed in the past to prepare such membranes. Radiation-induced graft copolymerization provides an attractive ft method for modification of chemical and physical properties of polymeric materials and is of particular interest in achieving specially desired cation exchange membranes as well as excellent membrane properties. This is due to the ability to control the membrane compositions as well as properties by proper selection of grafting conditions. Therefore numerous parameters have to be investigated to properly select the right polymeric materials, radiation grafting technique and the grafting conditions to be employed. In this paper a state-of-the-art of radiation-induced graft copolymerization for preparation of cation exchange membranes and their applications are briefly reviewed. (Author)

Radiation induced graft copolymerization of methyl methacrylate onto chrome-tanned pig skins

International Nuclear Information System (INIS)

Pietrucha, K.; Pekala, W.; Kroh, J.

1981-01-01

Graft copolymerization of methyl methacrylate (MMA) onto chrome-tanned pig skins was carried out by irradiation with 60 Co γ-rays. The grafted polymethyl methacrylate (PMMA) chains were isolated by acid hydrolysis of the collagen backbone in order to characterize the graft copolymers. Proof of grafting was obtained through the detection of amino acid endgroups in the isolated grafts by reaction with ninhydrin. The grafting yield of MMA in aqueous emulsion was found to be higher than that for pure MMA and MMA in acetone. The degree of grafting increases with increasing monomer concentration in emulsion and reaches maximum at radiation dose ca 15 kGy. The yield of grafting is very high. The present paper reports the physical properties of chrome-tanned pig skins after graft polymerization with MMA in emulsion. Modified leathers are more resistant against water absorption and abrasion in comparison with unmodified ones. They have more uniform structure over the whole surface, greater thickness and stiffness. The mechanism of some of the processes occurring during radiation grafting of MMA in water emulsion on tanned leathers has been also suggested and discussed. (author)

Photocrosslinkable Star Polymers via RAFT-Copolymerizations with N-Ethylacrylate-3,4-dimethylmaleimide

Directory of Open Access Journals (Sweden)

Philipp Vana

2013-06-01

Full Text Available This paper describes the Z-RAFT-star copolymerization of n-butyl acrylate (BA and N-isopropyl acrylamide (NIPAm, respectively, with N-ethylacrylate-3,4-dimethylmaleimide (1.1, a monomer carrying a UV-reactive unit that undergoes photocrosslinking. Addition of 1.1 slows down the polymerization rate both for BA and for NIPAm polymerization. Double star formation due to radical attack to the 3,4-dimethylmaleimide moiety was found in the case of BA. Dead polymer formation, presumably due to aminolysis as side-reaction, was pronounced in the NIPAm system. These two effects broadened the molar mass distributions, but did not impede the formation of functional star polymers. The composition of the copolymers as well as the reactivity ratios for the applied comonomers were determined via NMR spectroscopy (BA-co-1.1 r1.1 = 2.24 rBA = 0.95; NIPAm-co-1.1 r1.1 = 0.96 rNIPAm = 0.05. In both cases, the comonomer is consumed preferably in the beginning of the polymerization, thus forming gradient copolymer stars with the UV-reactive units being located in the outer sphere.

Radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene in flow system, 10

International Nuclear Information System (INIS)

Watanabe, Hiromasa; Ito, Masayuki; Okamoto, Jiro; Machi, Sueo.

1982-02-01

Radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene by continuous operation was carried out using a flow apparatus with tank type reactor of 5 liter under a constant pressure of 30 kg/cm 2 , a temperature of 40 0 C, and a propylene fraction in monomer gas of 0.1. The polymer concentration in latex reaches to steady value after two times longer operation than mean residence time of latex in the reactor. The steady polymer concentration increases accelerately with increase of the mean residence time. The polymer concentrations and the polymerization rates are 33, 70, 164 g/l-H 2 O and 35.1, 40.0, 49.5 g/h.l-H 2 O, respectively, obtained at the mean residence times of 0.94, 1.75 and 3.31 hour. The results are consistent with those in semi-batch operation under the same reaction conditions. The amounts of dissolved monomer in latex tends to decrease with decreasing the mean residence time. This shows that monomer supply by diffusion from gas phase to latex is not enough in shorter residence time of latex in the reactor. (author)

Radiation induced graft copolymerization of methyl methacrylate onto chrome-tanned pig skins

Energy Technology Data Exchange (ETDEWEB)

Pietrucha, K.; Pekala, W.; Kroh, J. (Lodz Univ. (Poland))

1981-01-01

Graft copolymerization of methyl methacrylate (MMA) onto chrome-tanned pig skins was carried out by irradiation with /sup 60/Co ..gamma..-rays. The grafted polymethyl methacrylate (PMMA) chains were isolated by acid hydrolysis of the collagen backbone in order to characterize the graft copolymers. Proof of grafting was obtained through the detection of amino acid endgroups in the isolated grafts by reaction with ninhydrin. The grafting yield of MMA in aqueous emulsion was found to be higher than that for pure MMA and MMA in acetone. The degree of grafting increases with increasing monomer concentration in emulsion and reaches maximum at radiation dose ca 15 kGy. The yield of grafting is very high. The present paper reports the physical properties of chrome-tanned pig skins after graft polymerization with MMA in emulsion. Modified leathers are more resistant against water absorption and abrasion in comparison with unmodified ones. They have more uniform structure over the whole surface, greater thickness and stiffness. The mechanism of some of the processes occurring during radiation grafting of MMA in water emulsion on tanned leathers has been also suggested and discussed.

Understanding organometallic reaction mechanisms and catalysis experimental and computational tools computational and experimental tools

CERN Document Server

Ananikov, Valentin P

2014-01-01

Exploring and highlighting the new horizons in the studies of reaction mechanisms that open joint application of experimental studies and theoretical calculations is the goal of this book. The latest insights and developments in the mechanistic studies of organometallic reactions and catalytic processes are presented and reviewed. The book adopts a unique approach, exemplifying how to use experiments, spectroscopy measurements, and computational methods to reveal reaction pathways and molecular structures of catalysts, rather than concentrating solely on one discipline. The result is a deeper

RAFT Polymerization of Styrene and Maleimide in the Presence of Fluoroalcohol: Hydrogen Bonding Effects with Classical Alternating Copolymerization as Reference

Directory of Open Access Journals (Sweden)

Fangjun Yao

2017-03-01

Full Text Available The impacts of hydrogen bonding on polymerization behavior has been of interest for a long time; however, universality and in-depth understanding are still lacking. For the first time, the effect of hydrogen bonding on the classical alternating-type copolymerization of styrene and maleimide was explored. N-phenylmaleimide (N-PMI/styrene was chosen as a model monomer pair in the presence of hydrogen bonding donor solvent 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP, which interacted with N-PMI via hydrogen bonding. Reversible addition-fragmentation chain transfer polymerization (RAFT technique was used to guarantee the “living” polymerization and thus the homogeneity of chain compositions. In comparison with the polymerization in nonhydrogen bonding donor solvent (toluene, the copolymerization in HFIP exhibited a high rate and a slight deviation from alternating copolymerization tendency. The reactivity ratios of N-PMI and St were revealed to be 0.078 and 0.068, respectively, while the reactivity ratios in toluene were 0.026 and 0.050. These interesting results were reasonably explained by using computer simulations, wherein the steric repulsion and electron induction by the hydrogen bonding between HFIP and NPMI were revealed. This work first elucidated the hydrogen bonding interaction in the classical alternating-type copolymerization, which will enrich the research on hydrogen bonding-induced polymerizations.

Graft copolymerization of N-vinyl-2-pyrrolidone onto pre-irradiated poly(vinylidene fluoride) powder

International Nuclear Information System (INIS)

Xu Chenqi; Huang Wei; Zhou Yongfeng; Yan Deyue; Chen Shutao; Huang Hua

2012-01-01

Graft copolymerization of N-vinyl-2-pyrrolidone (NVP) onto 60 Co γ-ray pre-irradiated poly (vinylidene fluoride) (PVDF) powder was investigated to find out the relationship between the degree of grafting (DG) and various factors, including monomer concentration, irradiation dose, reaction time, catalyst and so on. The DG can be calculated by comparing the amount of nitrogen element in the resulting copolymer (PVDF-g-PVP) powder with that in PVP on the basis of element analysis. The presence of PVP in the resulting PVDF powder was confirmed by the comparative studies of pristine PVDF and grafted PVDF powder through Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS), thermo gravimetric analyzer (TGA) and differential scanning calorimetry (DSC), respectively. When the reaction was performed at the monomer concentration of 20% (vol.) and the absorbed dose of 40 kGy for 3 h in water, the max. DG of 17.7% was obtained. - Highlights: ► We modify pristine PVDF powders with NVP by the pre-irradiated graft polymerization. ► The various factors influencing the degree of grafting are investigated in detail. ► The optimal condition of graft polymerization is obtained. ► The polymerization is processed at 20% (vol.) of NVP and 40kGy for 3 hours in water. ► The maximum degree of grafting is 17.7 % at such a condition.

Effect of acid additives on graft copolymerization and water absorption of graft copolymers of cassava starch and acrylamide/acrylic acid

International Nuclear Information System (INIS)

Kiatkamjornwong, Suda; Mongkolsawat, Kanlaya; Sonsuk, Manit

2003-01-01

Gelatinized cassava starch was radiation graft copolymerized with acrylamide or acrylic acid in the presence of sulfuric acid, nitric acid or maleic acid at a specific dose rate to a fixed total dose. Homopolymer or free copolymer was extracted by water to obtain the pure graft copolymer, which was subsequently saponified with 5% potassium hydroxide solution at room temperature for 90 min. The saponified graft copolymer was investigated for the effect of acid additives and water absorption. The addition of 2% maleic acid into the grafting reaction containing acrylamide-to-starch ratio of 2.5:1 can produce the superabsorbent copolymer having water absorption as high as 2,256 ± 25 g g -1 . The effect of acid additive was explained. (author)

Experimental Study of Na based Titanium Nanofluid-Water Reaction

Energy Technology Data Exchange (ETDEWEB)

Park, Gunyeop; Kim, Soo Jae; Baek, Jehyun; Kim, Hyun Soo; Oh, Sun Ryung; Park, Hyun Sun; Kim, Moo Hwan [POSTECH, Pohang (Korea, Republic of)

2015-10-15

In KALIMER-600, a sodium-cooled fast reactor designed by KAERI, thermal energy is transported from high-temperature liquid Na (526 .deg. C at 0.1 MPa) to low temperature water (230 .deg. C at - 19.5 MPa) through a heat exchanger. If any leakage or rupture occurs during the operation of this heat exchanger, highly pressurized liquid water can penetrate into the liquid Na channels; this contact should instantly cause SWR. As reaction continues, liquid water is soon vaporized by pressure drop and huge amount of reaction heat. This generated water vapor expands large reaction area and increases sodium-water vapor reaction process. Therefore, the rapid generation of reaction product (like H{sub 2}) and water vapor increases the system pressure that can cause the system failure in SFR. To reduce this strong chemical reaction phenomena between Na and water, some we have focused on suppressing the chemical reactivity of liquid Na by dispersing nanoparticles (NPs). For the real application of NaTiNF, the pressure change induced by NaTiNF-water reaction is compared with Na-water reaction in the present study. NaTiNF contains 100nm of Ti NPs at 0.2 vol. %. The reaction rate of NaTiNF-water reaction is also investigated as reaction temperature increases. Sodium-water vapor reaction (SVR) will occur when an SWR accident occurs in SFR. In this manner, NaTiNF-water vapor reaction is experimentally performed for ensuring the suppression of chemical reactivity of NaTiNF in contact with water vapor. In the basic step for reducing risk of an SWR in SFR, we have experimentally verified the suppressed chemical reactivity of liquid sodium using Ti NPs through SWR and SVR experiments. In SWR, Na based titanium nanofluid (NaTiNF) shows lower pressure change than Na. As T{sub R} increases, P{sub max} in Na-water reaction increases while NaTiNF does not. The reaction rate of NaTiNF shows twice slower than that of Na. In SVR, NaTiNF shows slower temperature increase than Na. The distinct

Reactivity of vinyl ethers and vinyl ribosides in UV-initiated free radical copolymerization with acceptor monomers.

Science.gov (United States)

Pichavant, Loic; Guillermain, Céline; Coqueret, Xavier

2010-09-13

The reactivity of various vinyl ethers and vinyloxy derivatives of ribose in the presence of diethyl fumarate or diethyl maleate was investigated for evaluating the potential of donor-acceptor-type copolymerization applied to unsaturated monomers derived from renewable feedstock. The photochemically induced polymerization of model monomer blends in the bulk state was monitored by infrared spectroscopy. The method allowed us to examine the influence of monomer pair structure on the kinetic profiles. The simultaneous consumption of both monomers was observed, supporting an alternating copolymerization mechanism. A lower reactivity of the blends containing maleates compared with fumarates was confirmed. The obtained kinetic data revealed a general correlation between the initial polymerization rate and the Hansen parameter δ(H) associated with the H-bonding aptitude of the donor monomer.

Recent experimental results on level densities for compound reaction calculations

International Nuclear Information System (INIS)

Voinov, A.V.

2012-01-01

There is a problem related to the choice of the level density input for Hauser-Feshbach model calculations. Modern computer codes have several options to choose from but it is not clear which of them has to be used in some particular cases. Availability of many options helps to describe existing experimental data but it creates problems when it comes to predictions. Traditionally, different level density systematics are based on experimental data from neutron resonance spacing which are available for a limited spin interval and one parity only. On the other hand reaction cross section calculations use the total level density. This can create large uncertainties when converting the neutron resonance spacing to the total level density that results in sizable uncertainties in cross section calculations. It is clear now that total level densities need to be studied experimentally in a systematic manner. Such information can be obtained only from spectra of compound nuclear reactions. The question is does level densities obtained from compound nuclear reactions keep the same regularities as level densities obtained from neutron resonances- Are they consistent- We measured level densities of 59-64 Ni isotopes from proton evaporation spectra of 6,7 Li induced reactions. Experimental data are presented. Conclusions of how level density depends on the neutron number and on the degree of proximity to the closed shell ( 56 Ni) are drawn. The level density parameters have been compared with parameters obtained from the analysis of neutron resonances and from model predictions

Experimental study of the role of nanoparticles in sodium–water reaction

International Nuclear Information System (INIS)

Park, Gunyeop; Kim, Soo Jae; Kim, Moo Hwan; Park, Hyun Sun

2014-01-01

Highlights: • We experimentally research the effect of nanoparticles in sodium–water reaction. • We present sodium–water reaction experiments and observed the mitigated reaction rate of sodium nanofluid. • We indicate nanoparticles settled on the surface of liquid sodium affect to mitigate chemical reactivity of sodium during sodium–water reaction. - Abstract: This paper presents an experimental study of the effect of Titanium (Ti) nanoparticles (NPs) on the mechanism of Sodium–Water chemical Reaction (SWR). Sodium–Titanium Nano Fluid (NaTiNF), i.e., liquid sodium that includes dispersed Ti NPs (≤100 nm) at 0.214 vol.% was produced. To simulate an accident in a sodium–water heat exchanger in a Sodium-cooled Fast Reactor, SWR was conducted by injecting liquid water directly onto the surface of liquid sodium. The reaction behavior of NaTiNF was quantitatively compared with that of bare sodium. Experiment results present that NaTiNF shows mitigated reactivity with water and lower reaction rate than bare sodium. These results imply that NPs dispersed in liquid sodium affect the mechanism of SWR

Emulsion (Co)polymerization of styrene and butyl acrylate monitored by On-line Raman Spectroscopy

NARCIS (Netherlands)

van den Brink, H.J.T.; Pepers, M.L.H.; Herk, van A.M.; German, A.L.

2000-01-01

The homo- and copolymerizations of styrene and n-butyl acrylate were studied by on-line in-situ Raman spectroscopy.Results from the solution (homo)polymerizations proved to be very useful in the quantification of the Raman data from the emulsion homopolymerization. From the homopolymerization data

Formation of network during radiation three-dimentional copolymerization of α, ω-dibutyl-bis-maleatetriethylene glycol with styrene

International Nuclear Information System (INIS)

Bol'bit, N.M.; Bol'shakova, T.A.; Fajzi, N.Kh.; Chikin, Yu.A.

1983-01-01

The radiation-induced copolymerization of α,ω-dibutyl-bis-maleatetriethylene glycol (dimaleate) with styrene in bulk has been studied for the ratio of initial molar concentrations of styrene to dimaleate being equal to 1.9. Initiation has been carried out using 60 Co gamma radiation with intensity 650 rad/s. Radiation doses are 3.5-16 Mrad. Up to approximately 18% conversion only soluble copolymer is formed. Per approximately 3.5 units of styrene in this copolymer 1 unit of dimaleate with one unreacted double bond is detected. Then in the narrow range of conversion the transformation of the main part soluble copolymer into macrogel proceeds. This fact is apparently the result of the change of physical state of the system alike the microphase separation resulting in essential increase of the probability of reaction between propagating radicals of neigh-- boring molecules and maleate bonds

Graft copolymerization of N-maleoyl-N-phthaloyl-chitosan (MAPHCS) and acrylic acid via γ-ray irradiation

International Nuclear Information System (INIS)

Mu Qing; Fang Yue'e

2006-01-01

Chitosan is a well-known abundant natural polymer with good biodegradability, biocompatibility and bioactivity. But its insolubility in common organic solvents of chitosan have hindered its utilization and basic research. N-maleoyl-N-phthaloyl-chitosan (MAPHCS), soluble in DMF or DMSO, was synthesized and characterized by Fourier transform infrared spectra analysis (FT-IR) and 1 H-NMR. The graft copolymerization of acrylic acid onto chitosan was carried out with N-maleoyl-N-phthaloyl-chitosan as intermediate in homogeneous system and initiated by γ-irradiation. The double bond of MAPHCS may be the grafting site because the grafting field was much higher than that of the graft copolymerization of acrylic acid and phthaloylchitosan via γ-ray irradiation. The chemical structure of the graft copolymer was characterized by FT-IR and 1 H-NMR. As indicated in FTIR spectra, the evidence of the stronger absorbance at 2800-3000 cm -1 for C-H and at 1720 cm -1 for carboxyl group implied significantly the successful introduction of the poly (acrylic acid) on the chitosan chain. Differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) were also used to characterize the copolymer. Effects of synthesis variables on the graft copolymerization were studied in light of the grafting percentage. The grafting percentage increased with the dose at lower doses, and then decreased. The maximum grafting percentage was up to 132%. (authors)

Copolymerization of Styrene and Methacrylates in the presence of Catalytic Chain Transfer Agents (Cacti's)

International Nuclear Information System (INIS)

Hussain, M.Sakhawat; Khan, M.A.; Ahmad, Shafique

2005-01-01

The present paper focuses on the use of a Co (II) complex, [Co(afdo-H)] as a catalytic chain transfer agent (CCTA) for controlling molecular weight in copolymerization of styrene (STY) with butyl methacrylate (BMA) and methylmethacrylate (MMA). The catalyst is structurally similar to [co(dmg-H) (BF)] patented by Du Pont as a CCTA. Average catalytic chain transfer constant, C8 of [co(afdo-H) (BF)] for coplymerization of STY with BMA and MMA determined from Maya plot, was found to be in the range of 10-10.This value is lower than the value reported for the [Co(dmg-H)(BF)). In the case of STY-BMA or STY-MMA copolymerization, a considerable reduction in the viscosity average molecular weights (Mv) was observed in the copolymers. The average molecular weight of poly (MMA-BMA) was reduced by a factor of ten compared to the reduction in poly (STY-MMA) and poly (STY-BMA) for the same concentration of the CCTA. (author)

Modification of natural leather by grafting emulsion copolymerization technique

International Nuclear Information System (INIS)

Badran, A.S.; Nasr, H.E.; El-Halawany, N.R.; Mohamed, W.S.

2005-01-01

Grafting emulsion copolymerization of methyl methacrylate (MMA) with butyl acrylate of different molar ratios onto natural leather with different molar ratios was carried out using developed redox initiation system of potassium persulphate (PPS) as an oxidizing agent and some sodium bisulphite adducts as reducing agent, as well as sodium dodecyl sulphate (SDS) was used as an anionic emulsifier. The grafted leather was characterized via FTIR, SEM and thermal gravimetric analysis. Moreover, the grafted leather was evaluated through water absorption, tensile strength, dyeing performance and hardness measurements. The obtained results revealed that the physical and mechanical properties of the modified leather were enhanced

Enhancement of deuteron-fusion reactions in metals and experimental implications

International Nuclear Information System (INIS)

Huke, A.; Heide, P.; Czerski, K.; Ruprecht, G.; Targosz, N.; Zebrowski, W.

2008-01-01

Recent measurements of the reaction 2 H(d,p) 3 H in metallic environments at very low energies performed by different experimental groups point to an enhanced electron screening effect. However, the resulting screening energies differ strongly for diverse host metals and different experiments. Here, we present new experimental results and investigations of interfering processes in the irradiated targets. These measurements inside metals set special challenges and pitfalls that make them and the data analysis particularly error prone. There are multiparameter collateral effects that are crucial for the correct interpretation of the observed experimental yields. They mainly originate from target surface contaminations owing to residual gases in the vacuum as well as from inhomogeneities and instabilities in the deuteron density distribution in the targets. To address these problems an improved differential analysis method beyond the standard procedures has been implemented. Profound scrutiny of the other experiments demonstrates that the observed unusual changes in the reaction yields are mainly due to deuteron density dynamics simulating the alleged screening energy values. The experimental results are compared with different theoretical models of the electron screening in metals. The Debye-Hueckel model that has been previously proposed to explain the influence of the electron screening on both nuclear reactions and radioactive decays can be clearly excluded

Copolymerization and terpolymerization of carbon dioxide/propylene oxide/phthalic anhydride using a (salenCo(III complex tethering four quaternary ammonium salts

Directory of Open Access Journals (Sweden)

Jong Yeob Jeon

2014-08-01

Full Text Available The (salenCo(III complex 1 tethering four quaternary ammonium salts, which is a highly active catalyst in CO2/epoxide copolymerizations, shows high activity for propylene oxide/phthalic anhydride (PO/PA copolymerizations and PO/CO2/PA terpolymerizations. In the PO/PA copolymerizations, full conversion of PA was achieved within 5 h, and strictly alternating copolymers of poly(1,2-propylene phthalates were afforded without any formation of ether linkages. In the PO/CO2/PA terpolymerizations, full conversion of PA was also achieved within 4 h. The resulting polymers were gradient poly(1,2-propylene carbonate-co-phthalates because of the drift in the PA concentration during the terpolymerization. Both polymerizations showed immortal polymerization character; therefore, the molecular weights were determined by the activity (g/mol-1 and the number of chain-growing sites per 1 [anions in 1 (5 + water (present as impurity + ethanol (deliberately fed], and the molecular weight distributions were narrow (Mw/Mn, 1.05–1.5. Because of the extremely high activity of 1, high-molecular-weight polymers were generated (Mn up to 170,000 and 350,000 for the PO/PA copolymerization and PO/CO2/PA terpolymerization, respectively. The terpolymers bearing a substantial number of PA units (fPA, 0.23 showed a higher glass-transition temperature (48 °C than the CO2/PO alternating copolymer (40 °C.

A Recyclable Nanoparticle-Supported Rhodium Catalyst for Hydrogenation Reactions

Directory of Open Access Journals (Sweden)

Maria Michela Dell’Anna

2010-05-01

Full Text Available Catalytic hydrogenation under mild conditions of olefins, unsaturated aldeydes and ketones, nitriles and nitroarenes was investigated, using a supported rhodium complex obtained by copolymerization of Rh(cod(aaema [cod: 1,5-cyclooctadiene, aaema–: deprotonated form of 2-(acetoacetoxyethyl methacrylate] with acrylamides. In particular, the hydrogenation reaction of halonitroarenes was carried out under 20 bar hydrogen pressure with ethanol as solvent at room temperature, in order to minimize hydro-dehalogenation. The yields in haloanilines ranged from 85% (bromoaniline to 98% (chloroaniline.

Analytical advantages of copolymeric microspheres for fluorimetric sensing - tuneable sensitivity sensors and titration agents.

Science.gov (United States)

Stelmach, Emilia; Maksymiuk, Krzysztof; Michalska, Agata

2017-01-15

Analytical benefits related to application of copolymeric microspheres containing different number of carboxylic acid mers have been studied on example of acrylate copolymers. These structures can be used as a reagent in heterogeneous pH titration, benefiting from different number of reactive groups - i.e. different concentration of a titrant - within the series of copolymers. Thus introducing the same amount of different microspheres from a series to the sample, different amount of the titrant is introduced. Copolymeric microspheres also can be used as optical sensors - in this respect the increasing number of reactive groups in the series is useful to improve the analytical performance of microprobes - sensitivity of determination or/and response range. The increase in ion-permeability of the spheres with increasing number of reactive mers is advantageous. It is shown that for pH sensitive microspheres containing higher number of carboxyl groups the higher sensitivity for alkaline pH samples is observed for an indicator present in the beads. The significant increase of optical responses is related to enhanced ion transport within the microspheres. For zinc or potassium ions model sensors tested it was shown that by choice of pH conditions and type of microspheres from the series, the optical responses can be tuned - to enhance sensitivity for analyte concentration change as well as to change the response pattern from sigmoidal (higher sensitivity, narrow range) to linear (broader response range). For classical optode systems (e.g. microspheres containing an optical transducer - pH sensitive dye and optically silent ionophore - receptor) copolymeric microspheres containing carboxylic acid mers in their structure allow application of the sensor in alkaline pH range, which is usually inaccessible for applied optical transducer. Copyright © 2016 Elsevier B.V. All rights reserved.

Radiation-induced copolymerizations of perfluorovinyl acetic acid and its methyl ester with α-olefin

International Nuclear Information System (INIS)

Kawaguchi, M.; Watanabe, T.; Matsuda, O.; Tabata, Y.; Machi, S.

1981-01-01

Homopolymerizations and copolymerizations of perfluorovinyl acetic acid (FVA) and its methyl ester (MFVA) were carried out by γ radiation at a temperature of 25 0 C, a dose rate of 1 x 10 6 rad/hr, and FVA/α-olefin and MFVA/α-olefin ratios of 10/90-90/10 in the monomer mixture. FVA and MFVA gave small quantities of brown and greasy low-molecular-weight homopolymers. The polymerization rates of both FVA and MFVA were extremely small, as shown by the maximum G value of monomer consumption of 12. FVA and MFVA reacted with α-olefin to form waxlike copolymers. The copolymerization rates of both FVA and MFVA with α-olefin were remarkably larger than those of the homopolymerizations, particularly with ethylene. The polymer compositions of FVA/ethylene or MFVA/ethylene were nearly 1/2 over a wide range of the monomer compositions. The Mayo-Lewis method gave negative r 1 (FVA) and r 1 (MFVA). The polymer composition curves could be well interpreted by introducing the penultimate model

A concise summary of experimental facts about the Soai reaction.

Science.gov (United States)

Gehring, Timo; Busch, Mark; Schlageter, Martin; Weingand, Daniel

2010-01-01

The Soai reaction amplifies small enantiomeric excesses in a spectacular manner. Being known for 20 years, it has drawn the attention of many scientists in different fields as it is to date the only chemical reaction offering the chance to study the phenomenon of asymmetric autocatalysis in conjunction with high amplification of enantiomeric excess (ee). This mini-review comprises an introduction to the discovery of asymmetric autocatalysis with amplification of ee and a concise summary of published experimental results showing which starting materials and reaction parameters play an important role in this reaction and which influences are understood. It is addressed especially to scientists entering the field of the Soai reaction to get a quick overview of important aspects. © 2010 Wiley-Liss, Inc.

Multifragment emission and the experimental characterization of breakup reactions

International Nuclear Information System (INIS)

Martinez Heimann, D.; Pacheco, A. J.; Arazi, A.; Fernandez Niello, J. O.; Figueira, J. M.; Negri, A.; Capurro, O. A.; Carnelli, P.; Cardona, M. A.; Barbara, E. de; Fimiani, L.; Hojman, D. L.; Marti, G. V.

2010-01-01

The production of three or more particles in nuclear reactions is discussed in terms of physically meaningful variables for the description of the asymptotic exit-channel configuration. The emphasis is placed in a direct comparison between these basic variables obtained in a purely experimental way and the corresponding results of generic model calculations. Applications of this approach to a few examples of recent inclusive and exclusive measurements of breakup reactions in the 6,7 Li+ 144 Sm systems are presented.

Gas Phase Homo- and Co-polymerization of Ethylene over Mg(O Et){sub 2}/T HF/Si Cl{sub 4}/Ti Cl{sub 4}/ Catalysts

Energy Technology Data Exchange (ETDEWEB)

Min-Chul, Chung [Korea Advanced Institute of Science and Techology., Taejeon (Korea, Republic of); Il, Kim [Univ. of Ulsan., Ulsan (Korea, Republic of); Jae-Ha, Kim [Korea Petrochemial Ind., Kyungnam (Korea, Republic of); Hong-Ki Choi [Korea Advanced Institute of Science and Technology., Taejeon (Korea, Republic of); Seung-Ihl, Woo

1994-08-01

Homo- and co-polymerization of ethylene were carried out in both gas and slurry phases over Mg(O Et)2/T HF/Si Cl{sub 4}/Ti Cl{sub 4}-Al Et{sub 3} catalysts in the range of temperature 20-70{sup o} C and pressure 2-10 psig. In gas phase polymerization, maximum activity was measured at the Al/Ti mole ratio of 377, and reaction rate dependence on Al Et{sub 3} concentration could be explained with the Langmuir-Hinshelwood adsorption model. Even though maximum activities were obtained at the same temperature, 60{sup o} C in both gas and slurry phases, overall activation energy was higher for the slurry phase(13 kCal/mol) than for the gas phase(4.7 kCal/mol) polymerization. The molecular weight behavior has been examined by measuring intrinsic viscosity. The molecular weight was increased as the ethylene pressure increased, and as the temperature and the concentration of Al Et{sub 3} and hydrogen decreased. Using two different co monomers(propylene and butene-1), the copolymerization of ethylene was carried out. The intrinsic viscosity and the melt index were decreased as co monomer concentration increased, and the maximum activity was observed when the concentration of comonomer is about 20 mol%. (author). 28 refs. 6 tabs. 13 figs.

An experimental and theoretical study of reaction steps relevant to the methanol-to-hydrocarbons reaction

Energy Technology Data Exchange (ETDEWEB)

Svelle, Stian

2004-07-01

The primary objective of the present work is to obtain new insight into the reaction mechanism of the zeolite catalyzed methanol-to-hydrocarbons (MTH) reaction. It was decided to use both experimental and computational techniques to reach this goal. An investigation of the n-butene + methanol system was therefore initiated. Over time, it became apparent that it was possible to determine the rate for the methylation of n-butene by methanol. The ethene and propene systems were therefore reexamined in order to collect kinetic information also for those cases. With the development of user-friendly quantum chemistry programs such as the Gaussian suite of programs, the possibility of applying quantum chemical methods to many types of problems has become readily available even for non-experts. When performing mechanistic studies, there is quite often a considerable synergy effect when combining experimental and computational approaches. The methylation reactions mentioned above turned out to be an issue well suited for quantum chemical investigations. The incentive for examining the halomethane reactivity was the clear analogy to the MTH reaction system. Alkene dimerization was also a reaction readily examined with quantum chemistry. As discussed in the introduction of this thesis, polymethylbenzenes, or their cationic counterparts, are suspected to be key intermediates in the MTH reaction. It was therefore decided to investigate the intrinsic reactivity of these species in the gas-phase by employing sophisticated mass spectrometric (MS) techniques in collaboration with the MS group at the Department of Chemistry, University of Oslo The data thus obtained will also be compared with results from an ongoing computational study on gas phase polymethylbenzenium reactivity. 6 papers presenting various studies are included. The titles are: 1) A Theoretical Investigation of the Methylation of Alkenes with Methanol over Acidic Zeolites. 2) A Theoretical Investigation of the

Preparation of supramolecular polymers by copolymerization of monomers containing quadruple hydrogen bonding units with regular monomers

NARCIS (Netherlands)

2004-01-01

The invention relates to the synthesis of polymers containing self-complementary quadruple hydrogen groups by copolymerizing monomers containing a quadruple hydrogen bonding group with one or more monomers of choice. The resulting polymers show unique new characteristics due to the presence of

In-situ radiation dosimetry based on radio-fluorogenic co-polymerization

International Nuclear Information System (INIS)

Warman, John M; Luthjens, Leonard H; Haas, Matthijs P de

2009-01-01

A fluorimetric method of radiation dosimetry is presented for which the intensity of the fluorescence of a (tissue equivalent) medium is linearly dependent on accumulated dose from a few Gray up to kiloGrays. The method is based on radio-fluorogenic co-polymerization (RFCP) in which a normally very weakly fluorescent molecule becomes highly fluorescent when incorporated into a (radiation-initiated) growing polymer chain. The method is illustrated with results of in-situ measurements within the chamber of a cobalt-60 irradiator. It is proposed that RFCP could form the basis for fluorimetric multi-dimensional dose imaging.

Current experimental situation in heavy-ion reactions

International Nuclear Information System (INIS)

Scott, D.K.

1978-06-01

A detailed survey of the present experimental situation in heavy-ion physics is presented. The discussion begins by considering the simple excitation of discrete states in elastic scattering, transfer, and compound-nucleus reactions; it then turns to more drastic perturbations of the nucleus high in the continuum through fusion, fission, and deeply inelastic scattering, and concludes with the (possibly) limiting asymptotic phenomena of relativistic heavy-ion collisions. 138 figures, 5 tables, 451 references

Copolymerization of 4-Acetylphenyl Methacrylate with Ethyl Methacrylate: Synthesis, Characterization, Monomer Reactivity Ratios, and Thermal Properties

Directory of Open Access Journals (Sweden)

Gamze Barim

2014-01-01

Full Text Available Methacrylates have high glass transition temperature (Tg values and high thermal stability. A new methacrylate copolymer, poly(4-acetylphenyl methacrylate-co-ethyl methacrylate (APMA-co-EMA, was synthesized. The thermal behaviors of copolymers were investigated by differential scanning calorimetry and thermogravimetric analysis. They behaved as new single polymers with single Tg’s and the thermal stability of the copolymers increased with increasing 4-acetylphenyl methacrylate (APMA fraction, leading to the manufacture of copolymers with desired Tg values. Structure and composition of copolymers for a wide range of monomer feed ratios were determined by Fourier transform infrared (FT-IR and 1H-nuclear magnetic resonance (1H-NMR spectroscopic techniques. Copolymerization reactions were continued up to 40% conversions. The monomer reactivity ratios for copolymer system were determined by the Kelen-Tüdös (ra(APMA=0.81; rb(EMA=0.61 and extended Kelen-Tüdös (ra=0.77; rb=0.54 methods and a nonlinear least squares (ra=0.74; rb=0.49 method.

Antibacterial Modification of Microcrystalline Cellulose by Grafting Copolymerization

Directory of Open Access Journals (Sweden)

Ying Liu

2015-11-01

Full Text Available Microcrystalline cellulose (MCC has the advantage of a high specific surface area as compared to that of conventional cellulose fibers. In this study the monomer methacrylamide (MAM was used to treat MCC by grafting copolymerization. SEM, FTIR, and solid 13C NMR were used to characterize the morphology and composition of MAM-g-MCC. After the chlorination of MAM-g-MCC with 10% sodium hypochlorite solution, the grafted MCC exhibited antibacterial activity as a result of the formation of N-Cl bonds. The thermal stability, antibacterial ability, and storage stability of chlorinated MAM-g-MCC were also studied. The results showed that the chlorinated MAM-g-MCC had excellent storage stability and could inactivate all S. aureus and E. coli O157:H7 within 10 min.

Copolymerization preparation of cationic cyclodextrin chiral stationary phases for drug enantioseparation in chromatography

OpenAIRE

sprotocols

2015-01-01

Authors: Ren-Qi Wang, Teng-Teng Ong, Ke Huang, Weihua Tang & Siu-Choon Ng ### Abstract We described a facile and effective protocol wherein radical copolymerization is employed to covalently bond cationic β-cyclodextrin (β-CD) onto silica particles with extended linkage, resulting in a chiral stationary phase (IMPCSP) that can be used for the enantioseparation of racemic drugs in both high-performance liquid chromatography (HPLC) and supercritical fluid chromatography (SFC). Starting ...

Lithium-Assisted Copolymerization of CO 2 /Cyclohexene Oxide: A Novel and Straightforward Route to Polycarbonates and Related Block Copolymers

KAUST Repository

Zhang, Dongyue

2016-03-23

A facile route toward alternating polycarbonates by anionic copolymerization of carbon dioxide (CO2) and cyclohexene oxide (CHO), using lithium halide or alkoxide as initiators and triisobutylaluminum (TiBA) as activator, is reported. α,ω-Heterobifunctional and α,ω-dihydroxypoly(cyclohexene carbonate)s (PCHC) as well as poly(CHC-co-CHO) copolymers with different carbonate composition could also be easily synthesized by adjusting the amount of TiBA or by adding inert lithium salts. The value of this initiating system also resides in the easy access to PSt-b-PCHC (PSt: polystyrene) and PI-b-PCHC (PI: polyisoprene) block copolymers which can be derived by mere one-pot sequential addition of styrene or dienes first and then of CO2 and CHO under the same experimental conditions. © 2016 American Chemical Society.

An experimental and theoretical study of reaction steps relevant to the methanol-to-hydrocarbons reaction

Energy Technology Data Exchange (ETDEWEB)

Svelle, Stian

2004-07-01

The primary objective of the present work is to obtain new insight into the reaction mechanism of the zeolite catalyzed methanol-to-hydrocarbons (MTH) reaction. It was decided to use both experimental and computational techniques to reach this goal. An investigation of the n-butene + methanol system was therefore initiated. Over time, it became apparent that it was possible to determine the rate for the methylation of n-butene by methanol. The ethene and propene systems were therefore reexamined in order to collect kinetic information also for those cases. With the development of user-friendly quantum chemistry programs such as the Gaussian suite of programs, the possibility of applying quantum chemical methods to many types of problems has become readily available even for non-experts. When performing mechanistic studies, there is quite often a considerable synergy effect when combining experimental and computational approaches. The methylation reactions mentioned above turned out to be an issue well suited for quantum chemical investigations. The incentive for examining the halomethane reactivity was the clear analogy to the MTH reaction system. Alkene dimerization was also a reaction readily examined with quantum chemistry. As discussed in the introduction of this thesis, polymethylbenzenes, or their cationic counterparts, are suspected to be key intermediates in the MTH reaction. It was therefore decided to investigate the intrinsic reactivity of these species in the gas-phase by employing sophisticated mass spectrometric (MS) techniques in collaboration with the MS group at the Department of Chemistry, University of Oslo The data thus obtained will also be compared with results from an ongoing computational study on gas phase polymethylbenzenium reactivity. 6 papers presenting various studies are included. The titles are: 1) A Theoretical Investigation of the Methylation of Alkenes with Methanol over Acidic Zeolites. 2) A Theoretical Investigation of the

Kinetics and thermodynamics of living copolymerization processes.

Science.gov (United States)

Gaspard, Pierre

2016-11-13

Theoretical advances are reported on the kinetics and thermodynamics of free and template-directed living copolymerizations. Until recently, the kinetic theory of these processes had only been established in the fully irreversible regime, in which the attachment rates are only considered. However, the entropy production is infinite in this regime and the approach to thermodynamic equilibrium cannot be investigated. For this purpose, the detachment rates should also be included. Inspite of this complication, the kinetics can be exactly solved in the regimes of steady growth and depolymerization. In this way, analytical expressions are obtained for the mean growth velocity, the statistical properties of the copolymer sequences, as well as the thermodynamic entropy production. The results apply to DNA replication, transcription and translation, allowing us to understand important aspects of molecular evolution.This article is part of the themed issue 'Multiscale modelling at the physics-chemistry-biology interface'. © 2016 The Author(s).

Investigation of factors affecting slurry copolymerization of acrylo nitrite-vinylacetate for preparation of acrylic fibers

International Nuclear Information System (INIS)

Hajian, M.; Tavakoli, T.; Azarnasab, M.; Hossepian, M.

2001-01-01

Since 1978, acrylic fibers have been prepared by slurry polymerization comprising of about 94% acrylonitrile (A N) and 6% methyl methacrylate (M A) as a comonomer to a make bulky polymer and improve the dye ability of acrylic fibers in a continuous process by redox initiator (potassium persulfate and ammonium, ferrous sulfate). The slurry polymer obtained after neutralization, washing and drying are converted to polymer powder. The polymer is dissolved in dimethyl formamide (Dmf) and converted to acrylic fibers. Since 1998, it has been suggested that M A may be replaced by vinylacetate (V Ac), because V Ac has properties like M A and is a monomer produced by Arak Petrochemical CO. Therefore, in this project A N and V Ac were polymerized under the same conditions of A N and M A copolymerization process. Many tests have been carried out on the resulted polymer such as IR, viscosity, particle size, Whiteness of polymer powder and similar results were obtained as in the for former copolymer. In this work some important factors such as concentration of V Ac, time and temperature of polymerization reaction and also speed of agitator have been optimized

Derivation of capture and reaction cross sections from experimental quasi-elastic and elastic backscattering probabilities

International Nuclear Information System (INIS)

Sargsyan, V.V.; Adamian, G.G.; Antonenko, N.V.; Gomes, P.R.S.

2014-01-01

We suggest simple and useful methods to extract reaction and capture (fusion) cross sections from the experimental elastic and quasi-elastic backscattering data.The direct measurement of the reaction or capture (fusion) cross section is a difficult task since it would require the measurement of individual cross sections of many reaction channels, and most of them could be reached only by specific experiments. This would require different experimental setups not always available at the same laboratory and, consequently, such direct measurements would demand a large amount of beam time and would take probably some years to be reached. Because of that, the measurements of elastic scattering angular distributions that cover full angular ranges and optical model analysis have been used for the determination of reaction cross sections. This traditional method consists in deriving the parameters of the complex optical potentials which fit the experimental elastic scattering angular distributions and then of deriving the reaction cross sections predicted by these potentials. Even so, both the experimental part and the analysis of this latter method are not so simple. In the present work we present a much simpler method to determine reaction and capture (fusion) cross sections. It consists of measuring only elastic or quasi-elastic scattering at one backward angle, and from that, the extraction of the reaction or capture cross sections can easily be performed. (author)

Optimizing Nuclear Reaction Analysis (NRA) using Bayesian Experimental Design

International Nuclear Information System (INIS)

Toussaint, Udo von; Schwarz-Selinger, Thomas; Gori, Silvio

2008-01-01

Nuclear Reaction Analysis with 3 He holds the promise to measure Deuterium depth profiles up to large depths. However, the extraction of the depth profile from the measured data is an ill-posed inversion problem. Here we demonstrate how Bayesian Experimental Design can be used to optimize the number of measurements as well as the measurement energies to maximize the information gain. Comparison of the inversion properties of the optimized design with standard settings reveals huge possible gains. Application of the posterior sampling method allows to optimize the experimental settings interactively during the measurement process.

Control of particle size by feed composition in the nanolatexes produced via monomer-starved semicontinuous emulsion copolymerization.

Science.gov (United States)

Sajjadi, Shahriar

2015-05-01

Conventional batch and semicontinuous emulsion copolymerizations often produce large particles whose size cannot be easily correlated with the comonomer feed compositions, and are to some degree susceptible to composition drift. In contrast, we found that copolymer nanolatexes made via semicontinuous monomer-starved emulsion copolymerizations are featured with an average nanoparticle size being controlled by the feed composition, a high conversion achieved, and a high degree of particle composition uniformity. This was achieved because the rate of particle growth, during nucleation, was controlled by the rate of comonomer addition, and the copolymer composition, surfactant parking area on the particles, and nucleation efficiency determined by the comonomer feed composition. Two model systems, methyl methacrylate/styrene and vinyl acetate/butyl acrylate, with significant differences in water solubility were studied. Monomers were added to the aqueous solution of sodium dodecylsulfate and potassium persulfate at a low rate to achieve high instantaneous conversions. Copyright © 2015 Elsevier Inc. All rights reserved.

Functional copolymer/organo-MMT nanoarchitectures. VI. Synthesis and characterization of novel nanocomposites by interlamellar controlled/living radical copolymerization via preintercalated RAFT-agent/organoclay complexes.

Science.gov (United States)

Rzayev, Zakir M O; Söylemez, A Ernur

2011-04-01

We have developed a new approach for the synthesis of polymer nanocomposites using a bifunctional reversible addition-fragmentation chain transfer (RAFT) agent, two types of organo-montmorillonites, such as a non-reactive dimethyldodecyl ammonium (DMDA)-MMT and a reactive octadecylamine (ODA)-MMT organoclays, and a radical initiator. The method includes the following stages: (1) synthesis of RAFT intercalated O-MMTs by a physical or chemical interaction of the RAFT agent having two pendant carboxylic groups [S,S-bis(alpha,alpha'-dimethyl-alpha"-acetic acid)trithiocarbonate] with surface alkyl amines of O-MMT containing tertiary ammonium cation or primary amine groups through strong H-bonding and complexing/amidization reactions, respectively, and (2) utilization of these well-dispersed and intercalated RAFT ... O-MMT complexes and their amide derivatives as new modified RAFT agents in radical-initiated interlamellar controlled/living copolymerization of itaconic acid (IA)-n-butylmethacrylate (BMA) monomer pair. The structure and compositions of the synthesized RAFT ... O-MMT complexes and functional copolymer/O-MMT hybrids were confirmed by FTIR, XRD, thermal (DSC-TGA), SEM and TEM morphology analyses. It was demonstrated that the degree of interaction/exfoliation, morphology and thermal behavior of nanocomposites significantly depended on the type of organoclay and in situ interaction, as well as on the content of flexible butyl-ester linkages as a internal plasticizer. The results of the comparative analysis of the nanocomposites structure-composition-property relations show that the functional copolymer-organoclay hybrids prepared with reactive RAFT ... ODA-MMT complex and containing a combination of partially intercalated and predominantly exfoliated nano-structures exhibit relatively higher thermal stability and fine dispersed morphology. These effects were explained by in situ interfacial chemical reactions through amidization of RAFT with surface alkyl amine

Swelling and thermodynamic studies of temperature responsive 2-hydroxyethyl methacrylate/itaconic acid copolymeric hydrogels prepared via gamma radiation

International Nuclear Information System (INIS)

Tomic, Simonida L.J.; Micic, Maja M.; Filipovic, Jovanka M.; Suljovrujic, Edin H.

2007-01-01

The copolymeric hydrogels based on 2-hydroxyethyl methacrylate (HEMA) and itaconic acid (IA) were synthesized by gamma radiation induced radical polymerization. Swelling and thermodynamic properties of PHEMA and copolymeric P(HEMA/IA) hydrogels with different IA contents (2, 3.5 and 5 mol%) were studied in a wide pH and temperature range. Initial studies of so-prepared hydrogels show interesting pH and temperature sensitivity in swelling and drug release behavior. Special attention was devoted to temperature investigations around physiological temperature (37 deg. C), where small changes in temperature significantly influence swelling and drug release of these hydrogels. Due to maximum swelling of hydrogels around 40 deg. C, the P(HEMA/IA) hydrogel containing 5 mol% of IA without and with drug-antibiotic (gentamicin) were investigated at pH 7.40 and in the temperature range 25-42 deg. C, in order to evaluate their potential for medical applications

Radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene in flow system, (9)

International Nuclear Information System (INIS)

Watanabe, Hiromasa; Ito, Masayuki; Okamoto, Jiro; Machi, Sueo.

1982-02-01

Seeded copolymerization of tetrafluoroethylene with propylene by radiation was carried out in a flow apparatus with pipe reactor at a pressure of 30 kg/cm 2 , a temperature of 40 0 C, a dose rate of 4.9 x 10 5 rad/h, and at various monomer compositions. Polymer concentration in latex increases linearly at propylene fraction of 0.25 and accelerately at the fraction below 0.1 with reaction time. The polymerization rates are 36, 60, 57, and 46 g/h.l-H 2 O at propylene fractions of 0.01, 0.05, 0.1, and 0.25, respectively. Fluorine content of the polymer obtained at the end of polymerization is 53.8 wt% at propylene fractions of 0.25 and 0.1, and is 56.5 wt% at the fraction of 0.01. For the insoluble polymer in tetrahydrofuran produced at the fraction of 0.01, the fluorine content is 61.3 wt%. This indicates that monomer unit ratio of tetrafluoroethylene and propylene is 1.8/l. In the polymerization at a region of high tetrafluoroethylene content in monomer gas, it was elucidated that alternative arrangement of copolymer being characteristic in this system is broken down to produce tetrafluoroethylene rich polymer, and polymerization rate is reduced. This is explained by that addition of propylene monomer to tetrafluoroethylene polymer radical becomes rate-determining step due to the extremely poor propylene concentration in polymer particles. (author)

Potassium diperiodatocuprate-mediated preparation of poly(methyl methacrylate/organo-montmorillonite composites via in situ grafting copolymerization

Directory of Open Access Journals (Sweden)

2008-09-01

Full Text Available In this study, potassium diperiodatocuprate (Cu3+ was selected as an initiator to prepare poly(methyl methacrylate/organo-montmorillonite composites (OMMT-g-PMMA by in situ graft copolymerization. Three synthetic parameters were systematically evaluated as a function of the temperature, the concentration of initiator, pH and the ratio of MMA to OMMT. It was found that Cu3+ was a highly efficient initiator for the preparation of OMMT-g-PMMA i.e., monomer conversion and grafting efficiency were as higher as 95%. The X-ray diffraction measurement showed the intercalation of PMMA chains into OMMT layers on base of an increasing basal spacing after polymerization. FTIR analysis also suggested that the PMMA chains were effectively grafted onto OMMT substrate. The enhanced thermal stabilities of OMMT-g-PMMA composites were confirmed by the thermal gravimetric analysis (TGA. Finally, a single-electron-transfer mechanism was proposed to illustrate the formation of radicals and the preparation process of OMMT-g-PMMA composites. Cu3+ can be used as an effective and practical initiator in preparing the organic/inorganic composite due to its high grafting efficiency and the milder reaction condition.

Experimental test of exchange degeneracy in hypercharge exchange reactions

International Nuclear Information System (INIS)

Moffeit, K.C.

1978-10-01

Two pairs of line-reversed reactions π + P → K + Σ + , K - p → π - Σ + and π + p → K + Y* + (1385), K - p → π - Y* + (1385) provide an experimental test of exchange degeneracy in hypercharge exchange reactions. From their study it is concluded that in contrast to the lower energy data, the 11.5 results for the two pairs of reactions are consistent with exchange degeneracy predictions for both helicity-flip and nonflip amplitudes. The Y(1385) decay angular distributions indicate that the quark model and Stodolsky--Sakurai predictions are in agreement with the main features of the data. However, small violations are observed at small momentum transfer. While the Y(1385) vertex is helicity-flip dominated, the nonvanishing of T/sub 3/2 - 1/2/ and T/sub -3/2 1/2/ suggests some finite helicity nonflip contribution in the forward direction. 23 references

Matching of experimental and statistical-model thermonuclear reaction rates at high temperatures

International Nuclear Information System (INIS)

Newton, J. R.; Longland, R.; Iliadis, C.

2008-01-01

We address the problem of extrapolating experimental thermonuclear reaction rates toward high stellar temperatures (T>1 GK) by using statistical model (Hauser-Feshbach) results. Reliable reaction rates at such temperatures are required for studies of advanced stellar burning stages, supernovae, and x-ray bursts. Generally accepted methods are based on the concept of a Gamow peak. We follow recent ideas that emphasized the fundamental shortcomings of the Gamow peak concept for narrow resonances at high stellar temperatures. Our new method defines the effective thermonuclear energy range (ETER) by using the 8th, 50th, and 92nd percentiles of the cumulative distribution of fractional resonant reaction rate contributions. This definition is unambiguous and has a straightforward probability interpretation. The ETER is used to define a temperature at which Hauser-Feshbach rates can be matched to experimental rates. This matching temperature is usually much higher compared to previous estimates that employed the Gamow peak concept. We suggest that an increased matching temperature provides more reliable extrapolated reaction rates since Hauser-Feshbach results are more trustwhorthy the higher the temperature. Our ideas are applied to 21 (p,γ), (p,α), and (α,γ) reactions on A=20-40 target nuclei. For many of the cases studied here, our extrapolated reaction rates at high temperatures differ significantly from those obtained using the Gamow peak concept

Experimental (Network) and Evaluated Nuclear Reaction Data at NDS

International Nuclear Information System (INIS)

Otsuka, N.; Semkova, V.; Simakov, S.P.; Zerkin, V.

2011-01-01

Dr Simakov of Nuclear Data Services Unit in the Nuclear Data Section (NDS) gave a brief overview of the data compilation and evaluation activities in the nuclear data community: experimental nuclear reaction data (EXFOR, http://www-nds.iaea.org/exfor/) and evaluated nuclear reaction data (ENDF, http://www-nds.iaea.org/endf). The International Network of Nuclear Reaction Data Centres (NRDC) coordinated by NDS includes 14 Centres in 8 Countries (China, Hungary, India, Japan, Korea, Russian, Ukraine, USA) and 2 International Organizations (NEA, IAEA). It had the first meeting of four core centres (Brookhaven, Saclay, Obninsk, Vienna) in 1966 and the EXFOR was adopted as an official data exchange format. In 2000, IAEA implemented the EXFOR database as a relational multiform database and the EXFOR is a trusted, increasing and living database with 19100 experimental works (as of September 2011) and 141600 data tables. The EXFOR provides a compilation control system for selection of articles and compilation of data and the NRDC home page provides manuals, documents and codes. The nuclear data can be retrieved by the web-retrieval system or distributed on a DVD on request. The EXFOR data play a critical role in the development of evaluated nuclear reaction data. There are several major general purpose libraries: ENDF (US), CENDL (China), JEFF (EU), JENDL (Japan) and RUSFOND (Russia). In addition, there are special libraries for particular applications: EAF (European Activation File), FENDL (Fusion Evaluated Nuclear Data Library for ITER neutronics), IBANDL (Ion Beam Analysis Nuclear Data Library for surface analysis of solids), IRDF, DXS (Dosimetry, radiation damage and gas production data) and Medical portal. Dr V. Zerkin of NDS demonstrated the data retrieval from the EXFOR database and the ENDF library.

Experimental (Network) and Evaluated Nuclear Reaction Data at NDS

Energy Technology Data Exchange (ETDEWEB)

Otsuka, N; Semkova, V; Simakov, S P; Zerkin, V [Nuclear Data Services Unit, Nuclear Data Section, IAEA, Vienna (Austria)

2011-11-15

Dr Simakov of Nuclear Data Services Unit in the Nuclear Data Section (NDS) gave a brief overview of the data compilation and evaluation activities in the nuclear data community: experimental nuclear reaction data (EXFOR, http://www-nds.iaea.org/exfor/) and evaluated nuclear reaction data (ENDF, http://www-nds.iaea.org/endf). The International Network of Nuclear Reaction Data Centres (NRDC) coordinated by NDS includes 14 Centres in 8 Countries (China, Hungary, India, Japan, Korea, Russian, Ukraine, USA) and 2 International Organizations (NEA, IAEA). It had the first meeting of four core centres (Brookhaven, Saclay, Obninsk, Vienna) in 1966 and the EXFOR was adopted as an official data exchange format. In 2000, IAEA implemented the EXFOR database as a relational multiform database and the EXFOR is a trusted, increasing and living database with 19100 experimental works (as of September 2011) and 141600 data tables. The EXFOR provides a compilation control system for selection of articles and compilation of data and the NRDC home page provides manuals, documents and codes. The nuclear data can be retrieved by the web-retrieval system or distributed on a DVD on request. The EXFOR data play a critical role in the development of evaluated nuclear reaction data. There are several major general purpose libraries: ENDF (US), CENDL (China), JEFF (EU), JENDL (Japan) and RUSFOND (Russia). In addition, there are special libraries for particular applications: EAF (European Activation File), FENDL (Fusion Evaluated Nuclear Data Library for ITER neutronics), IBANDL (Ion Beam Analysis Nuclear Data Library for surface analysis of solids), IRDF, DXS (Dosimetry, radiation damage and gas production data) and Medical portal. Dr V. Zerkin of NDS demonstrated the data retrieval from the EXFOR database and the ENDF library.

In Vitro and In Vivo Characterization of Biodegradable Reactive Isocyanate-Terminated Three-Armed- and Hyperbranched Block Copolymeric Tissue Adhesives

NARCIS (Netherlands)

Bochynska, Agnieszka I.; Hannink, Gerjon; Rongen, Jan J.; Grijpma, Dirk W.; Buma, Pieter

2017-01-01

Tissue adhesives are an attractive class of biomaterials, which can serve as a treatment for meniscus tears. In this study, physicochemical and adhesive properties of novel biodegradable three-armed- and hyperbranched block copolymeric adhesives are evaluated. Additionally, their degradation in

Radiation graft copolymerization of styrene with m/e and styrene with acrylic acid at highthyl methacryl dose rate

International Nuclear Information System (INIS)

Aliev, R.Eh.; Kabanov, B.Ya.

1984-01-01

Comparative investigation of radiation graft copolymerization of styrene with methyl methacrylate (MMA) and styrene with acrylic acid (AA) is carried out at considerably differing radiation dose rates. The monomer mixture was grafted to PE low density films at dose rates of 0.16, 0.25 Gy/s (1 MeV electron acceleration). The value of graft was 3-6 and 5-10%, respectively, for the styrene-MMA and styrene-AA systems. An essential difference in the dependences of the formed copolymer composition on initial monomer mixture composition is noticed. Difference in composition of graft polymers prepared at different dose rates is less for the systems with AA, than for systems with MMA. It is shown that at high dose rates in difference with low ones not only radical graft copolymerization of the styrene mixture with AA takes place, but a contribution of the graft styrene polymerization according to cation mechanism as well

Study on curing reaction of 4-aminophenoxyphthalonitrile/bisphthalonitrile

Institute of Scientific and Technical Information of China (English)

Xiao

2010-01-01

A series of phthalonitrile blending resins were prepared from 4-aminophenoxyphthalonitrile (APN) and 4,4'-bis (3,4-dicyanophenoxy)biphenyl (BPH) by directly powder-mixing and copolymerization. Differential scanning calorimeter (DSC) and dynamic rheology were used to study the curing reaction behaviors of APN/BPH blends, and the results indicated that the introduction of APN accelerated the curing rate of BPH, and the existence of BPH decreased the curing temperature of APN/BPH systems. The thermal stability of postcured APN/BPH resins was investigated by thermogravimetric analysis (TGA), and the TGA results indicated that the crosslinked polymers of APN/BPH systems possessed good thermal stability.

RAFT copolymerization of itaconic anhydride and 2-methoxyethyl acrylate: a multifunctional scaffold for preparation of “clickable” gold nanoparticles

DEFF Research Database (Denmark)

Javakhishvili, Irakli; Kasama, Takeshi; Jankova, Katja Atanasova

2013-01-01

RAFT copolymerization of 2-methoxyethyl acrylate and itaconic anhydride – a monomer derived from renewable resources – is carried out in a controlled fashion. The copolymer allows preparation of gold nanoparticles with abundant surficial carboxyl and alkyne functional groups that are dendronized...

Monomers capable of forming four hydrogen bridges and supramolecular polymers formed by copolymerization of these monomers with regular monomers

NARCIS (Netherlands)

2004-01-01

The invention relates to the synthesis of polymers containing self-complementary quadruple hydrogen groups by copolymerizing monomers containing a quadruple hydrogen bonding group with one or more monomers of choice. The resulting polymers show unique new characteristics due to the presence of

Summary Report of the Workshop on the Experimental Nuclear Reaction Data Database

International Nuclear Information System (INIS)

Semkova, V.; Pritychenko, B.

2014-12-01

The Workshop on the Experimental Nuclear Reaction Data Database (EXFOR) was held at IAEA Headquarters in Vienna from 6 to 10 October 2014. The workshop was organized to discuss various aspects of the EXFOR compilation process including compilation rules, different techniques for nuclear reaction data measurements, software developments, etc. A summary of the presentations and discussions that took place during the workshop is reported here. (author)

Summary Report of the Workshop on The Experimental Nuclear Reaction Data Database

Energy Technology Data Exchange (ETDEWEB)

Semkova, V. [IAEA Nuclear Data Section, Vienna (Austria); Pritychenko, B. [Brookhaven National Lab. (BNL), Upton, NY (United States)

2014-12-01

The Workshop on the Experimental Nuclear Reaction Data Database (EXFOR) was held at IAEA Headquarters in Vienna from 6 to 10 October 2014. The workshop was organized to discuss various aspects of the EXFOR compilation process including compilation rules, different techniques for nuclear reaction data measurements, software developments, etc. A summary of the presentations and discussions that took place during the workshop is reported here.

Synthesis and Study of Shape-Memory Polymers Selectively Induced by Near-Infrared Lights via In Situ Copolymerization

Directory of Open Access Journals (Sweden)

Tianyu Fang

2017-05-01

Full Text Available Shape-memory polymers (SMPs selectively induced by near-infrared lights of 980 or 808 nm were synthesized via free radical copolymerization. Methyl methacrylate (MMA monomer, ethylene glycol dimethylacrylate (EGDMA as a cross-linker, and organic complexes of Yb(TTA2AAPhen or Nd(TTA2AAPhen containing a reactive ligand of acrylic acid (AA were copolymerized in situ. The dispersion of the organic complexes in the copolymer matrix was highly improved, while the transparency of the copolymers was negligibly influenced in comparison with the pristine cross-linked PMMA. In addition, the thermal resistance of the copolymers was enhanced with the complex loading, while their glass transition temperature, cross-linking level, and mechanical properties were to some extent reduced. Yb(TTA2AAPhen and Nd(TTA2AAPhen provided the prepared copolymers with selective photothermal effects and shape-memory functions for 980 and 808 nm NIR lights, respectively. Finally, smart optical devices which exhibited localized transparency or diffraction evolution procedures were demonstrated based on the prepared copolymers, owing to the combination of good transparency and selective light wavelength responsivity.

Experimental specifications for eutectic reaction between metallic fuel and HT-9

International Nuclear Information System (INIS)

Hwang, Woan; Nam, Cheol; Lee, Byoung Oon; Ryu, Woo Seog

1998-10-01

The chemical interaction between metallic fuel and cladding is important in designing the fuel pin of the KALIMER. When metal fuel and cladding are contacted, the elements in fuel and cladding are inter-diffuse each other, forming the reaction layers at interface. The reaction layers may cause two important factors in aspects of fuel pin integrity. Firstly, it degrades cladding strength by reducing effective cladding thickness. Secondly, these layers accelerate eutectic reaction at transient conditions. To evaluate these phenomena, the diffusion couple experiment is planned by using metal fuels with various zirconium contents and HT-9 steel. The U-Zr fuel alloys will be used for the experiment with the different zirconium contents, these are 8, 10 and 12 weight %. This experiment aims to evaluate the effects of zirconium content on the chemical reaction. Furthermore, the reaction rate and threshold temperature of the eutectic melting will be determined as a function of the zirconium content. This document describes the detail experimental specifications for the eutectic reaction such as test setup, test requirements and test procedure. (author). 10 refs

Graft copolymerization of polystyrene onto chitosan congress as an adsorbent for the removal of heavy metal ions

International Nuclear Information System (INIS)

Dela Mines, Remedel D.; Muncal, Danilet Vi A.

2013-01-01

Chitosan is primarily composed of glucosamine, 2-amino-2-deoxy-β-D-glucose. Chitosan has different types of reactive functional groups. Both hydroxyl and amino groups are possible sites for the reaction to incorporate new and desired functional groups. By modification of these groups various materials for different field of application can be achieved. Chitosan has been used as adsorbent for the removal of heavy metal ions from aqueous solution through adsorption process. Properties of chitosan, such as solubility, mechanical stability and adsorption compatibility, are enhanced by grafting. In this study, chitosan was graft copolymerized with polystyrene for wastewater treatment and evaluated its effectiveness in removing toxic heavy metals by adsorption. Chitosan-graft-polystyrene was characterized by FTIR spectroscopy, and SEM. Adsorption study of the copolymer is carried out as a function of adsorbent dose, pH, and contact time. Residual concentration was measured by Atomic Absorption Spectroscopy. To get an insight of the rate of adsorption and the rate limiting step of the transport mechanism, kinetic analysis was utilized. Langmuir equation/isotherm was used for proper quantification of the sorption equilibrium in the bio sorption process (author)

Status of experimental data of proton-induced reactions for intermediate-energy nuclear data evaluation

Energy Technology Data Exchange (ETDEWEB)

Watanabe, Yukinobu; Kawano, Toshihiko [Kyushu Univ., Fukuoka (Japan); Yamano, Naoki; Fukahori, Tokio

1998-11-01

The present status of experimental data of proton-induced reactions is reviewed, with particular attention to total reaction cross section, elastic and inelastic scattering cross section, double-differential particle production cross section, isotope production cross section, and activation cross section. (author)

Phosphine-Thiophenolate Half-Titanocene Chlorides: Synthesis, Structure, and Their Application in Ethylene (Co-Polymerization

Directory of Open Access Journals (Sweden)

Yue-Sheng Li

2013-03-01

Full Text Available A series of novel half-titanocene complexes CpTiCl2[S-2-R-6-(PPh2C6H3] (Cp = C5H5, 2a, R = H; 2b, R = Ph; 2c, R = SiMe3 have been synthesized by treating CpTiCl3 with the sodium of the ligands, 2-R-6-(PPh2C6H3SNa, which were prepared by the corresponding ligands and NaH. These complexes have been characterized by 1H, 13C and 31P NMR as well as elemental analyses. Structures for 2a–b were further confirmed by X-ray crystallography. Complexes 2a–b adopt five-coordinate, distorted square-pyramid geometry around the titanium center, in which the equatorial positions are occupied by sulfur and phosphorus atoms of the chelating phosphine-thiophenolate and two chlorine atoms, and the cyclopentadienyl ring is coordinated on the axial position. The complexes 2a–c were investigated as the catalysts for ethylene polymerization and copolymerization of ethylene with norbornene in the presence of MMAO or Ph3CB(C6F54/iBu3Al as the cocatalyst. All complexes exhibited low to moderate activities towards homopolymerization of ethylene. However, they displayed moderate to high activities towards copolymerization of ethylene with norbornene.

Graft copolymerization of a series of alkyl acrylates and alkyl methacrylates onto polyethylene

International Nuclear Information System (INIS)

Zurakowska-Orszagh, J.; Soerjosoeharto, K.; Busz, W.; Oldziejewski, J.

1977-01-01

Graft copolymerization of a series of alkyl acrylates and alkyl methacrylates into polyethylene of Polish production was investigated, using benzoyl peroxide as the initiator as well as preirradiation technique, namely ionizing radiation from a 60 Co γ-source. The effect of α-carbon methyl substituent of methacrylates as well as the influence of the length of alkyl chains in the ester groups of both series of monomers into the grafting process was observed. The ungrafted and some of the grafted polyethylene film obtained was studied by infrared spectrophotometry. (author)

Experimental and phenomenological comparison between Piezonuclear reactions and Condensed Matter Nuclear Science phenomenology

OpenAIRE

Cardone, F.; Mignani, R.; Petrucci, A.

2011-01-01

The purpose of this paper is to place side by side the experimental results of Piezonu- clear reactions, which have been recently unveiled, and those collected during the last twenty years of experiments on low energy nuclear reactions (LENR). We will briefy re- port the results of our campaign of piezonuclear reactions experiments where ultrasounds and cavitation were applied to solutions of stable elements. These outcomes will be shown to be compatible with the results and evidences obtaine...

Discussion of the experimental methods of the estimation of the reaction impact parameter

International Nuclear Information System (INIS)

Muryn, B.; Dziunikowska, K.; Eskreys, A.; Coghen, T.

1978-01-01

Two methods of determination of the reaction impact parameter, the one proposed by Webber and other by Henyey and Pumplin, are compared and discussed. It is shown that the lower limits of the impact parameter bsub(L) obtained by means of these methods are comparable and are always very low (approximately < 0.5 fm). On the example of the Henyey - Pumplin method it is argued that the experimentally obtained values bsub(L) may be very unreliable estimates of the reaction impact parameter and that any comparison of different reactions or reactions channels may be meaningless. (author)

Metallocene-catalyzed ethylene−α-olefin isomeric copolymerization: A perspective from hydrodynamic boundary layer mass transfer and design of MAO anion

KAUST Repository

Adamu, Sagir; Atiqullah, Muhammad; Malaibari, Zuhair O.; Al-Harthi, Mamdouh A.; Emwas, Abdul-Hamid M.; Ul-Hamid, Anwar

2015-01-01

-catalyzed ethylene polymerization. This approach was illustrated by conducting homo- and isomeric copolymerization of ethylene with 1-hexene and 4-methyl-1-pentene in the presence of bis(n-butylcyclopentadienyl) zirconium dichloride (nBuCp)2ZrCl2, using (i) MAO anion

Parameters Effect on Productivity

Directory of Open Access Journals (Sweden)

S. Ahmadjo

2010-12-01

Full Text Available Bis(indenylzirconium dichloride as a catalyst was synthesized using a modified method at the room temperature. Polymerization of ethylene and copolymerization of ethylene and propylene were carried out by this metallocene catalyst. Ethylene propylene (P/E feed ratios of 0.25, 0.5, 1, and 2 were employed into the copolymerization systems. Copolymerization conditions like cocatalyst/catalyst ratio, copolymerization temperature, feed ratio and the viscosity average molecular weight (Mv changing with copolymerization temperature were investigated. Higher ratio of [Al]/[Zr]=750:1 increased the activity of the catalyst. However, higher concentration of the cocatalyst slightly reduced the activity. Viscosity-average molecular weight of polymer decreased with high ratio of [Al]/[Zr]. The highest activity was obtained at 60oC. Increases in copolymerization temperature decreased the viscosity-average molecular weight and ethylene content of the polymeric products. Increases in propylene content of the feed ratio producedamorphous polymers with products of increased glass transition temperatures.Kinetic reaction displayed a decay type of reaction.

An experimental study on tissue reaction of various contrast agents on mediastinum

International Nuclear Information System (INIS)

Chung, Jin Wook; Kim, Hyung Jin; Kim, Seung Hyup; Park, Jae Hyung; Chang, Kee Hyun

1989-01-01

Till now, there is no consensus about appropriate contrast agents for use in clinical investigation in suspected perforation of the esophagus. Gastrografin, most widely used water soluble contrast agent, is less sensitive in detection of fistulous tract and can induce pulmonary edema, leading to death occasionally, if aspirated. Barium sulphate has been contraindicated without actual evaluation of its effect on mediastinum by experimental and clinical study. The purpose of this experimental study is to evaluate the type of tissue reaction and its severity in mediastinum and, as a result, to propose appropriate contrast agents in various clinical situations of suspected esophageal leakage. Barium sulphate, Hytrat, Gastrografin, Telebrix, Hexabrix, Amipaque, Niopam, and Ultravist were injected into mediastinum of 20 rats in each. The tissue reaction of injection sites were examined microscopically and graded according severity of inflammatory reaction with serial follow up from 1 day to 8 weeks after injection. The results are as follows, 1. Barium sulphate and Hytrast produced highly significant (p<0.01) tissue reaction compared to saline group and early inflammatory reaction was more severe in Hytrast. 2. Water soluble agents produced no significant reaction in mediastinum compared to saline control group and proved to be safe in the situation of leakage into mediastinum. 3. Injected barium caused no death during 8 week follow up in spite of large injected amount and histologically produced localized indolent granuloma after 4 weeks which is expected not to cause any delayed complications. In consideration of above results, superior physical characteristics of barium sulphate and drawbacks of Gastrografin, we concluded as follows. 1. For postoperative assessment of esophageal anastomosis, Barium sulphate is the contrast agent of choice

Regulating Molecular Aggregations of Polymers via Ternary Copolymerization Strategy for Efficient Solar Cells.

Science.gov (United States)

Wang, Qian; Wang, Yingying; Zheng, Wei; Shahid, Bilal; Qiu, Meng; Wang, Di; Zhu, Dangqiang; Yang, Renqiang

2017-09-20

For many high-performance photovoltaic materials in polymer solar cells (PSCs), the active layers usually need to be spin-coated at high temperature due to the strong intermolecular aggregation of donor polymers, which is unfavorable in device repeatability and large-scale PSC printing. In this work, we adopted a ternary copolymerization strategy to regulate polymer solubility and molecular aggregation. A series of D-A 1 -D-A 2 random polymers based on different acceptors, strong electron-withdrawing unit ester substituted thieno[3,4-b]thiophene (TT-E), and highly planar dithiazole linked TT-E (DTzTT) were constructed to realize the regulation of molecular aggregation and simplification of device fabrication. The results showed that as the relative proportion of TT-E segment in the backbone increased, the absorption evidently red-shifted with a gradually decreased aggregation in solution, eventually leading to the active layers that can be fabricated at low temperature. Furthermore, due to the excellent phase separation and low recombination, the optimized solar cells based on the terpolymer P1 containing 30% of TT-E segment exhibit high power conversion efficiency (PCE) of 9.09% with a significantly enhanced fill factor up to 72.86%. Encouragingly, the photovoltaic performance is insensitive to the fabrication temperature of the active layer, and it still could maintain high PCE of 8.82%, even at room temperature. This work not only develops the highly efficient photovoltaic materials for low temperature processed PSCs through ternary copolymerization strategy but also preliminarily constructs the relationship between aggregation and photovoltaic performance.

Reversion of pH-induced physiological drug resistance: a novel function of copolymeric nanoparticles.

Directory of Open Access Journals (Sweden)

Rutian Li

Full Text Available AIMS: The extracellular pH of cancer cells is lower than the intracellular pH. Weakly basic anticancer drugs will be protonated extracellularly and display a decreased intracellular concentration. In this study, we show that copolymeric nanoparticles (NPs are able to overcome this "pH-induced physiological drug resistance" (PIPDR by delivering drugs to the cancer cells via endocytosis rather than passive diffussion. MATERIALS AND METHODS: As a model nanoparticle, Tetradrine (Tet, Pka 7.80 was incorporated into mPEG-PCL. The effectiveness of free Tet and Tet-NPs were compared at different extracellular pHs (pH values 6.8 and 7.4, respectively by MTT assay, morphological observation and apoptotic analysis in vitro and on a murine model by tumor volume measurement, PET-CT scanning and side effect evaluation in vivo. RESULTS: The cytotoxicity of free Tet decreased prominently (P<0.05 when the extracellular pH decreased from 7.4 to 6.8. Meanwhile, the cytotoxicity of Tet-NPs was not significantly influenced by reduced pH. In vivo experiment also revealed that Tet-NPs reversed PIPDR more effectively than other existing methods and with much less side effects. CONCLUSION: The reversion of PIPDR is a new discovered mechanism of copolymeric NPs. This study emphasized the importance of cancer microenvironmental factors in anticancer drug resistance and revealed the superiority of nanoscale drug carrier from a different aspect.

Ethylene homo- and copolymerization chain-transfers: A perspective from supported (n BuCp) 2 ZrCl 2 catalyst active centre distribution

KAUST Repository

Atiqullah, Muhammad; Al-Harthi, Mamdouh A.; Anantawaraskul, Siripon; Emwas, Abdul-Hamid M.

2015-01-01

/MAO/(nBuCp)2ZrCl2 - were applied to evaluate the active-centre-dependent ethylene homo- and copolymerization rates, as well as the corresponding chain termination rates. This approach, from a microkinetic mechanistic viewpoint, elucidates better the 1-hexene

System Identification for Experimental Study for Polymerization Catalyst Reaction in Fluidized Bed

Directory of Open Access Journals (Sweden)

Ahmmed Saadi Ibrehem

2011-11-01

Full Text Available In this work, system identification method is used to capture the reactor characteristics of production rate of polyethylene (PE based on published experimental data. The identification method is used to measure the percentage effect on the production rate of PE by measuring the effect of input factors of temperature of reaction, hydrogen concentration, and [Al]/[Ti] molar catalyst ratio. Temperature of reaction has big effects equal 52.4 % on the output of the system and 47.6 % on interaction of the system's parameters compare to other two factors. Also, hydrogen concentration has big effect equal 45.66 % on the output of the system and 14.7 % on interaction of the system's parameters. [Al]/[Ti] molar catalyst ratio has big effect on interaction of the system equal 28.6 and 1.94 % on the output of the system but less than the reaction temperature and hydrogen concentration. All these results depend on experiment results and these results are very important in industrial plants. ©2011 BCREC UNDIP. All rights reserved(Received: 13rd May 2011; Revised: 27th July 2011; Accepted: 22th September 2011[How to Cite: Ahmmed S. Ibrehem. (2011. System Identification for Experimental Study for Polymerization Catalyst Reaction in Fluidized Bed. Bulletin of Chemical Reaction Engineering & Catalysis, 6 (2: 137-146. doi:10.9767/bcrec.6.2.874.137-146][How to Link / DOI: http://dx,doi.org/10.9767/bcrec.6.2.874.137-146 || or local:  http://ejournal.undip.ac.id/index.php/bcrec/article/view/874 ] | View in 

Flexible Polymeric Materials Prepared by Radiation Copolymerization of MMA/ Pyridene in the Presence of Acrylic Acid

International Nuclear Information System (INIS)

Hegazy, D.E.

2014-01-01

Gamma-irradiation initiated copolymerization of methyl methacrylate (MMA) and pyridine (Py) was carried out at room temperature.To improve the obtained copolymer functionality and molecular weight, acrylic acid (AA) was incorporated into the mixture during irradiation. The samples were characterized by thermal analysis techniques (DSC and TGA), Fourier transform infrared spectroscopy (FTIR) and UV-VIS spectrometry. Molecular weight of the obtained copolymers was determined using gel permeation chromatography (GPC). The variation of refractive index and surface hardness with the molecular weight were also investigated. The results obtained show a decrease in glass transition temperature and the hardness (shore D) of the supporting matrix for P(MMA/Py) copolymers with a pronounced increase of the molecular weight. The addition of PAA into the matrix enhanced the hardness and shifts the glass transition temperature to a little higher temperature with a pronounced decrease in the melting temperature. The obtained materials maintain good structural order and flexibility resulting from the softening effect of pyridine onto MMA matrix. The studies performed made possible the selection of experimental conditions to be adequate for the production of new co polymeric materials with high molecular weight that having good flexibility and transparent properties.

Ionic membranes obtained by radiation-induced graft copolymerization, I-preparation. Vol. 3

Energy Technology Data Exchange (ETDEWEB)

Abd El-Rehim, H A; Hegazy, E A [National Center for Radiation and Technology, Atomic Energy Authority, Cairo, (Egypt); Ali, A M.I.; Nowier, H G; Aly, H F [Hot Laboratories Center, atomic Energy Authority, Cairo, (Egypt)

1996-03-01

A study has been made on the preparation of ionic membranes by radiation-induced graft copolymerization of acrylic acid (AAC) onto low density polyethylene (LDPE) films. The Suitable conditions at which the grafting proceeds homogeneously were determined. To minimize the homo polymerization of AAC during irradiation process different types of inhibitors were investigated to find that the addition of Fe Cl{sub 3} (1.5 Wt%) effectively reduced such process when compared with other inhibitors used. The suitable diluent for this grafting system is found to be distilled water, methanol and methanol water mixture. The effect of diluent mixture composition, irradiation time, addition of mineral or organic acid and metal chlorides on the grafting yield and its homogeneity in the graft copolymer was determined. It was observed that the grafting yield increased as the content of water increased in MeOH/H{sub 2} O mixture. The addition of oxalic acid to the reaction medium enhanced the grafting process, however, the addition of HCl or H{sub 2} S O{sub 4} resulted in a more homogeneous grafting. The same effect was also observed when metal salts; namely N H{sub 4} Cl, NaCl and Cu Cl{sub 2} were added and resulted in homogeneous grafted membranes. The swelling and permeability of the grafted films prepared were also investigated. Results obtained in this study showed a great promise for the possible practical use of such prepared graft copolymers as a good hydrophilic membrane. The possibility of its use as an ion-exchange membrane for metal waste will be considered.4 figs., 5 tabs.

Copolymerization of Phenylselenide-Substituted Maleimide with Styrene and Its Oxidative Elimination Behavior

Directory of Open Access Journals (Sweden)

Qian Liu

2018-03-01

Full Text Available Selenium-containing monomer monophenyl maleimide selenide (MSM was synthesized and copolymerized with styrene (St using reversible addition-fragmentation chain transfer (RAFT polymerization. Copolymers with controlled molecular weight and narrow molecular weight distribution were obtained. The structure of the copolymer was characterized by nuclear magnetic resonance, matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF mass spectrum, Fourier transform infrared spectroscopy (FT-IR and Ultraviolet–visible spectroscopy (UV-vis spectroscopy. The copolymer can be oxidized by H2O2 to form carbon-carbon double bonds within the main chain due to the unique sensitivity of selenide groups in the presence of oxidants. Such structure changing resulted in an interesting concentration-related photoluminescence emission enhancement.

The reaction between iodine and organic coatings under severe PWR accident conditions. An experimental parameter study

Energy Technology Data Exchange (ETDEWEB)

Hellmann, S; Funke, F; Greger, G U; Bleier, A; Morell, W [Siemens AG, Power Generation Group, Erlangen (Germany)

1996-12-01

An extensive experimental parameter study was performed on the deposition and on the resuspension kinetics in the reaction system iodine/organically coated surfaces. Both reactions in the gas phase and in the liquid phase were investigated and kinetic rate constants suitable for modelling were derived. Previous experimental studies on the reaction of iodine with organic coated surfaces were mostly limited to temperatures below 100{sup o}C. Thus, this parameter study aims at filling a gap and providing kinetic data on heterogeneous reactions with organic surfaces in the accident-relevant temperature range of 100-160{sup o}C. Two types of laboratory experiments carried out at Siemens/KWU using coatings representative for German power plants (epoxy-tape paint), namely gas phase tests and liquid phase tests. (author) 6 figs., 6 tabs., 5 refs.

Surface treatment of poly(ethylene terephthalate) by gamma-ray induced graft copolymerization of methyl acrylate and its toughening effect on poly(ethylene terephthalate)/elastomer blend

International Nuclear Information System (INIS)

Ma, Liang; Wang, Mozhen; Ge, Xuewu

2013-01-01

To improve the compatibility between ethylene-methyl acrylate-glycidyl methacrylate random terpolymer (E-MA-GMA) elastomer and poly(ethylene terephthalate) (PET), thereby enhance the toughening effect of E-MA-GMA on PET, γ-radiation-induced graft copolymerization technique was used to graft methyl acrylate (MA) monomer onto PET. The produced PET-g-PMA copolymer can be used as a self-compatibilizer in PET/E-MA-GMA blend since the copolymer contains the same segments, respectively, with PET and E-MA-GMA. The impact strength of PET/E-MA-GMA blend increased nearly by 30% in the presence of less than 0.1 wt% PET-g-PMA compared with that of the neat PET/elastomer blend, without loss of the tensile strength of the blends. This work proposed a potential application of radiation-induced grafting copolymerization technique on the in-situ compatibilization of PET/elastomer blends so as to improve the integral mechanical properties of PET based engineering plastic. - Highlights: • PMA was grafted onto PET resins by γ-ray radiation-induced copolymerization. • The obtained PET-g-PMA can improve the compatibility between PET and E-MA-GMA. • A small amount of PET-g-PMA can enhance the impact strength of PET/E-MA-GMA blend

Study of n-Butyl Acrylate Self-Initiation Reaction Experimentally and via Macroscopic Mechanistic Modeling

Directory of Open Access Journals (Sweden)

Ahmad Arabi Shamsabadi

2016-04-01

Full Text Available This paper presents an experimental study of the self-initiation reaction of n-butyl acrylate (n-BA in free-radical polymerization. For the first time, the frequency factor and activation energy of the monomer self-initiation reaction are estimated from measurements of n-BA conversion in free-radical homo-polymerization initiated only by the monomer. The estimation was carried out using a macroscopic mechanistic mathematical model of the reactor. In addition to already-known reactions that contribute to the polymerization, the model considers a n-BA self-initiation reaction mechanism that is based on our previous electronic-level first-principles theoretical study of the self-initiation reaction. Reaction rate equations are derived using the method of moments. The reaction-rate parameter estimates obtained from conversion measurements agree well with estimates obtained via our purely-theoretical quantum chemical calculations.

Experimental Cross Sections for Reactions of Heavy Ions and 208Pb, 209Bi, 238U, and 248Cm Targets

International Nuclear Information System (INIS)

Patin, Joshua B.

2002-01-01

The study of the reactions between heavy ions and 208 Pb, 209 Bi, 238 U, and 248 Cm targets was performed to look at the differences between the cross sections of hot and cold fusion reactions. Experimental cross sections were compared with predictions from statistical computer codes to evaluate the effectiveness of the computer code in predicting production cross sections. Hot fusion reactions were studied with the MG system, catcher foil techniques and the Berkeley Gas-filled Separator (BGS). 3n- and 4n-exit channel production cross sections were obtained for the 238 U( 18 O,xn) 256-x Fm, 238 U( 22 Ne,xn) 260-x No, and 248 Cm( 15 N,xn) 263-x Lr reactions and are similar to previous experimental results. The experimental cross sections were accurately modeled by the predictions of the HIVAP code using the Reisdorf and Schaedel parameters and are consistent with the existing systematics of 4n exit channel reaction products. Cold fusion reactions were examined using the BGS. The 208 Pb( 48 Ca,xn) 256-x No, 208 Pb( 50 Ti,xn) 258-x Rf, 208 Pb( 51 V,xn) 259-x Db, 209 Bi( 50 Ti,xn) 259-x Db, and 209 Bi( 51 V,xn) 260-x Sg reactions were studied. The experimental production cross sections are in agreement with the results observed in previous experiments. It was necessary to slightly alter the Reisdorf and Schaedel parameters for use in the HIVAP code in order to more accurately model the experimental data. The cold fusion experimental results are in agreement with current 1n- and 2n-exit channel systematics

EXFOR – a global experimental nuclear reaction data repository: Status and new developments

Directory of Open Access Journals (Sweden)

Semkova Valentina

2017-01-01

Full Text Available Members of the International Network of Nuclear Reaction Data Centres (NRDC have collaborated since the 1960s on the worldwide collection, compilation and dissemination of experimental nuclear reaction data. New publications are systematically complied, and all agreed data assembled and incorporated within the EXFOR database. Recent upgrades to achieve greater completeness of the contents are described, along with reviews and adjustments of the compilation rules for specific types of data.

Experimental Study of Serpentinization Reactions

Science.gov (United States)

Cohen, B. A.; Brearley, A. J.; Ganguly, J.; Liermann, H.-P.; Keil, K.

2004-01-01

Current carbonaceous chondrite parent-body thermal models [1-3] produce scenarios that are inconsistent with constraints on aqueous alteration conditions based on meteorite mineralogical evidence, such as phase stability relationships within the meteorite matrix minerals [4] and isotope equilibration arguments [5, 6]. This discrepancy arises principally because of the thermal runaway effect produced by silicate hydration reactions (here loosely called serpentinization, as the principal products are serpentine minerals), which are so exothermic as to produce more than enough heat to melt more ice and provide a self-sustaining chain reaction. One possible way to dissipate the heat of reaction is to use a very small parent body [e.g., 2] or possibly a rubble pile model. Another possibility is to release this heat more slowly, which depends on the alteration reaction path and kinetics.

Uncertainties and understanding of experimental and theoretical results regarding reactions forming heavy and superheavy nuclei

Science.gov (United States)

Giardina, G.; Mandaglio, G.; Nasirov, A. K.; Anastasi, A.; Curciarello, F.; Fazio, G.

2018-02-01

Experimental and theoretical results of the PCN fusion probability of reactants in the entrance channel and the Wsur survival probability against fission at deexcitation of the compound nucleus formed in heavy-ion collisions are discussed. The theoretical results for a set of nuclear reactions leading to formation of compound nuclei (CNs) with the charge number Z = 102- 122 reveal a strong sensitivity of PCN to the characteristics of colliding nuclei in the entrance channel, dynamics of the reaction mechanism, and excitation energy of the system. We discuss the validity of assumptions and procedures for analysis of experimental data, and also the limits of validity of theoretical results obtained by the use of phenomenological models. The comparison of results obtained in many investigated reactions reveals serious limits of validity of the data analysis and calculation procedures.

Raman spectroscopy of poly (3-hydroxybutyrate) modified with poly (vinyl acetate) by radiation- induced copolymerization

International Nuclear Information System (INIS)

Gonzalez, Maykel; Galego Fernandez, Norma; Ortiz del Toro, Pedro; Rapado, Manuel; Paredes

2007-01-01

Poly (3-hydroxybutyrate) (PHB) is an important material used in the field of medicine. However in common conditions, PHB has some deficiencies. It is very brittle and slightly hydrophobic polymer. This somewhat limit its applications. Radiation chemistry can be used to improve its chemical properties. In the present study, the substrate, modified by radiation-induced graft copolymerization with vinyl acetate (VAc), was characterized using FTIR and Raman spectroscopy. FTIR spectroscopy did not reveal any significant bands but Raman spectroscopy revealed the formation of a new band that characterize the material

Radiation crosslinking of poly(butyl acrylate) during polymerization and grafted copolymerization with Cr(III) crosslinked collagen

International Nuclear Information System (INIS)

Pietrucha, K.; Kroh, J.

1984-01-01

Enhanced crosslinking of synthetic polymer simultaneous with grafting and homopolymerization processes have been observed in irradiated leather tanned with Cr(III) and embedded with aqueous emulsions of butyl acrylate. Extent of poly(butyl acrylate) crosslinking during copolymerization was found to be approximately one order higher than in the case of radiation polymerization of butyl acrylate in emulsion. New method for isolation of grafted copolymer based on degradation of collagen has been developed. The extent of crosslinking was calculated from the swelling data. (author)

An experimental and theoretical study of reaction mechanisms between nitriles and hydroxylamine.

Science.gov (United States)

Vörös, Attila; Mucsi, Zoltán; Baán, Zoltán; Timári, Géza; Hermecz, István; Mizsey, Péter; Finta, Zoltán

2014-10-28

The industrially relevant reaction between nitriles and hydroxylamine yielding amidoximes was studied in different molecular solvents and in ionic liquids. In industry, this procedure is carried out on the ton scale in alcohol solutions and the above transformation produces a significant amount of unexpected amide by-product, depending on the nature of the nitrile, which can cause further analytical and purification issues. Although there were earlier attempts to propose mechanisms for this transformation, the real reaction pathway is still under discussion. A new detailed reaction mechanistic explanation, based on theoretical and experimental proof, is given to augment the former mechanisms, which allowed us to find a more efficient, side-product free procedure. Interpreting the theoretical results obtained, it was shown that the application of specific imidazolium, phosphonium and quaternary ammonium based ionic liquids could decrease simultaneously the reaction time while eliminating the amide side-product, leading to the targeted product selectively. This robust and economic procedure now affords a fast, selective amide free synthesis of amidoximes.

Silica-supported (nBuCp)2ZrCl2: Effect of catalyst active center distribution on ethylene-1-hexene copolymerization

KAUST Repository

Atiqullah, Muhammad

2013-08-12

Metallocenes are a modern innovation in polyolefin catalysis research. Therefore, two supported metallocene catalysts-silica/MAO/(nBuCp)2ZrCl2 (Catalyst 1) and silica/nBuSnCl3/MAO/(nBuCp)2ZrCl2 (Catalyst 2), where MAO is methylaluminoxane-were synthesized, and subsequently used to prepare, without separate feeding of MAO, ethylene-1-hexene Copolymer 1 and Copolymer 2, respectively. Fouling-free copolymerization, catalyst kinetic stability and production of free-flowing polymer particles (replicating the catalyst particle size distribution) confirmed the occurrence of heterogeneous catalysis. The catalyst active center distribution was modeled by deconvoluting the measured molecular weight distribution and copolymer composition distribution. Five different active center types were predicted for each catalyst, which was corroborated by successive self-nucleation and annealing experiments, as well as by an extended X-ray absorption fine structure spectroscopy report published in the literature. Hence, metallocenes impregnated particularly on an MAO-pretreated support may be rightly envisioned to comprise an ensemble of isolated single sites that have varying coordination environments. This study shows how the active center distribution and the design of supported MAO anions affect copolymerization activity, polymerization mechanism and the resulting polymer microstructures. Catalyst 2 showed less copolymerization activity than Catalyst 1. Strong chain transfer and positive co-monomer effect-both by 1-hexene-were common. Each copolymer demonstrated vinyl, vinylidene and trans-vinylene end groups, and compositional heterogeneity. All these findings were explained, as appropriate, considering the modeled active center distribution, MAO cage structure repeat units, proposed catalyst surface chemistry, segregation effects and the literature that concerns and supports this study. While doing so, new insights were obtained. Additionally, future research, along the direction

Silica-supported (nBuCp)2ZrCl2: Effect of catalyst active center distribution on ethylene-1-hexene copolymerization

KAUST Repository

Atiqullah, Muhammad; Anantawaraskul, Siripon; Emwas, Abdul-Hamid M.; Al-Harthi, Mamdouh Ahmed; Hussain, Ikram; Ul-Hamid, Anwar; Hossaen, Anwar

2013-01-01

Metallocenes are a modern innovation in polyolefin catalysis research. Therefore, two supported metallocene catalysts-silica/MAO/(nBuCp)2ZrCl2 (Catalyst 1) and silica/nBuSnCl3/MAO/(nBuCp)2ZrCl2 (Catalyst 2), where MAO is methylaluminoxane-were synthesized, and subsequently used to prepare, without separate feeding of MAO, ethylene-1-hexene Copolymer 1 and Copolymer 2, respectively. Fouling-free copolymerization, catalyst kinetic stability and production of free-flowing polymer particles (replicating the catalyst particle size distribution) confirmed the occurrence of heterogeneous catalysis. The catalyst active center distribution was modeled by deconvoluting the measured molecular weight distribution and copolymer composition distribution. Five different active center types were predicted for each catalyst, which was corroborated by successive self-nucleation and annealing experiments, as well as by an extended X-ray absorption fine structure spectroscopy report published in the literature. Hence, metallocenes impregnated particularly on an MAO-pretreated support may be rightly envisioned to comprise an ensemble of isolated single sites that have varying coordination environments. This study shows how the active center distribution and the design of supported MAO anions affect copolymerization activity, polymerization mechanism and the resulting polymer microstructures. Catalyst 2 showed less copolymerization activity than Catalyst 1. Strong chain transfer and positive co-monomer effect-both by 1-hexene-were common. Each copolymer demonstrated vinyl, vinylidene and trans-vinylene end groups, and compositional heterogeneity. All these findings were explained, as appropriate, considering the modeled active center distribution, MAO cage structure repeat units, proposed catalyst surface chemistry, segregation effects and the literature that concerns and supports this study. While doing so, new insights were obtained. Additionally, future research, along the direction

Microwave plasma initiated graft copolymerization modification of monomers onto PTFE surface

International Nuclear Information System (INIS)

Guan Weishu; Wen Yunjian; Fang Yan; Yin Yongxiang

1996-02-01

A graft copolymerization modification technique of monomers onto polytetrafluoroethylene (PTFE) surface initiated by a 2.45 GHz non-equilibrium microwave plasma has been investigated. Standard X-Ray Photoelectron Spectroscopy (XPS), Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR), Scanning Electron Microscopy (sEM) and wetting techniques were used for examination and analysis of samples. Considerable changes in chemical structure, composition and in morphology of grafted surface of PTFE were found. Results showed the occurrence of noticeable defluorination and cross-linked structure on grafted surface, and indicated that different kinds and contents of oxygen-containing functional groups were introduced into the surface of PTFE. Wetting and adhesion experiment of the sample proved that significant improvements in hydrophilicity and adhesion of surface were exhibited. These results confirmed the success of grafting. (8 refs., 7 figs., 1 tab.)

Radiation crosslinking of poly(butyl acrylate) during polymerization and grafted copolymerization with Cr(III) crosslinked collagen

International Nuclear Information System (INIS)

Pietrucha, K.; Kroh, J.

1986-01-01

Enhanced crosslinking of synthetic polymer simultaneously with grafting and homopolymerization processes has been observed in irradiated leather tanned with Cr(III) and embedded with aqueous emulsions of butyl acrylate. The extent of poly(butyl acrylate) crosslinking during copolymerization was found to be approximately one order higher than in the case of radiation polymerization of butyl acrylate in emulsion. A new method for isolation of grafted copolymer based on degradation of collagen has been developed. The extent of crosslinking was calculated from the swelling data. (author)

Graft Copolymerization Of Methyl Methacrylate Onto Agave Cellulose

International Nuclear Information System (INIS)

Noor Afizah Rosli; Ishak Ahmad; Ibrahim Abdullah; Farah Hannan Anuar

2014-01-01

The grafting polymerization of methyl methacrylate (MMA) and Agave cellulose was prepared and the grafting reaction conditions were optimized by varying the reaction time and temperature, and ratio of monomer to cellulose. The resulting graft copolymers were characterized by Fourier transform infrared, X-ray diffraction analysis, thermogravimetric analysis, and scanning electron microscopy (SEM). The experimental results showed that the optimal conditions were at a temperature of 45 degree Celsius for 90 min with ratio monomer to cellulose at 1:1 (g/ g). An additional peak at 1738 cm -1 which was attributed to the C=O of ester stretching vibration of poly(methyl methacrylate), appeared in the spectrum of grafted Agave cellulose. A slight decrease of crystallinity index upon grafting was found from 0.74 to 0.68 for cellulose and grafted cellulose, respectively. Grafting of MMA onto cellulose enhanced its thermal stability and SEM observation further furnished evidence of grafting MMA onto Agave cellulose with increasing cellulose diameter and surface roughness. (author)

Armature reaction effects on a high temperature superconducting field winding of an synchronous machine: experimental results

DEFF Research Database (Denmark)

Mijatovic, Nenad; Jensen, Bogi Bech

2014-01-01

This paper presents experimental results from the Superwind laboratory setup. Particular focus in the paper has been placed on describing and quantifying the influence of armature reaction on performance of the HTS filed winding. Presented experimental results have confirmed the HTS field winding...

An experimental approach to angular momentum transfer in heavy ion reactions

International Nuclear Information System (INIS)

Babinet, R.

1980-01-01

The current experimental status on angular momentum transfer status in heavy ion reactions is reviewed. After a short presentation of the basic theoretical concepts that are underlying all the research works in this field, the experimental techniques that have been commonly used are presented. Results obtained by the γ-multiplicity method are discussed first. Then come, for the very heavy systems, the sequential fission data, followed by the results of a recent experiment on light charged particles. The simple theoretical concepts that are introduced first are continuously used as guidelines to discuss the following results. The respective advantages but also the basic limitations of the above three experimental techniques are exposed. Although they are expected to work best in different regions of the mass table, it is shown, that they give complementary informations which have been most useful in improving our understanding of the tangential friction mechanism

Experimental and theoretical data on ion-molecule-reactions relevant for plasma modelling

International Nuclear Information System (INIS)

Hansel, A.; Praxmarer, C.; Lindinger, W.

1995-01-01

Despite the fact that the rate coefficients of hundreds of ion-molecule-reactions have been published in the literature, much more data are required for the purpose of plasma modelling. Many ion molecule reactions have rate coefficients, k, as large as the collisional limiting value, k c , i.e. the rate coefficients k c at which ion-neutral collision complexes are formed are close to the actual rate coefficients observed. In the case of the interaction of an ion with a non polar molecule, k c , is determined by the Langevin limiting value k L being typically 10 -9 cm 3 s -1 . However, when ions react with polar molecules k c is predicted by the average dipole orientation (ADO) theory. These classical theories yield accurate rate coefficients at thermal and elevated temperatures for practically all proton transfer as well as for many charge transfer and hydrogen abstraction reactions. The agreement between experimental and calculated values is usually better than ±20% and in the case of proton transfer reactions the agreement seems to be even better as recent investigations have shown. Even the interaction of the permanent ion dipole with non polar and polar neutrals can be taken into account to predict reaction rate coefficients as has been shown very recently in reactions of the highly polar ion ArH 3 + with various neutrals

Experimental studies of water hammer in propellant feed system of reaction control system

Directory of Open Access Journals (Sweden)

Avanish Kumar

2018-03-01

Full Text Available Water hammer pressure transient produces large dynamic forces which can damage the pipes and other assemblies in the feed line of a reaction control system (RCS. It has led to the failure of pressure transducers monitoring the manifold pressure in the feed line of RCS. Therefore, water hammer studies have been carried out to understand its effect in feed line. Feedline system has been simplified to develop a mathematical model and experiments have been carried out at extensive levels. The mathematical model was developed considering pipe of uniform c/s and moving liquid-gas interface. The experimental studies have been done using water as working medium instead of actual propellant. The studies showed that rate of pressurization have a very critical role on the water hammer amplitude. Sensitivity studies have been also carried out to study the effect of density, friction and initial liquid column length on water hammer amplitude. Keywords: Water hammer, Reaction control system (RCS, Propellant feed system, Experimental study, Testing

Theoretical and experimental methods to determine the properties of molten core components and reaction products. Pt. 2

International Nuclear Information System (INIS)

Nazare, S.; Ondracek, G.; Schulz, B.

1975-10-01

In the course of a loss of coolant accident, a sequence of events would be initiated that ultimately could lead to core melting. The course of these events and the consequences of core meltdown would in part be determined by the properties of the core materials and the products of their interaction. On the basis of available theoretical and experimental results, the report attempts an estimation of properties such as: 1) work of adhesion between UO 2 - and (U,Zr) liquid phase, 2) heat of fusion of some melts, 3) heat capacity of liquid reaction products, 4) viscosity of liquid reaction products, 5) thermal conductivity of liquid reaction products. Experimental work is suggested for those cases, where the estimates need to be improved or verified. (orig.) [de

Thermodynamic analysis and experimental study on the chlorination of uranium oxide by gas-solid reaction

International Nuclear Information System (INIS)

Shin, Y.J.; Kim, I.S.; Shin, H.S.; Ro, S.G.; Park, H.S.

1998-01-01

In order to determine the operating condition of an uranium chlorination process with U 3 O 8 -C-Cl 2 system, the experimental conditions have been evaluated preliminarily by the thermochemical analysis and experimentally confirmed in this study. The dry-type chlorination of U 3 O 8 occurs as irreversible and exothermic reaction and produces many kinds of chloride compounds such as UCl 3 , UCl 4 , UCl 5 , and UCl 6 in the air and humidity controlled argon environment. Taking account of Gibbs free energy and vapor pressure for various chloride compounds, the proper temperature range of chlorination appears to be 863 to 953 K in aspects of increasing reaction rate and the yield of nonvolatile product. In the course of the experimental confirmation the powder of U 3 O 8 is perfectly converted into uranium chlorides within 4 hours above 863 K, and then the maximum fraction of uranium chloride remaining in the reactor is about 30% of total conversion mass. (author)

Experimental studies of keV energy neutron-induced reactions relevant to astrophysics and nuclear physics

Energy Technology Data Exchange (ETDEWEB)

Shima, T.; Kii, T.; Kikuchi, T.; Okazaki, F.; Kobayashi, T.; Baba, T.; Nagai, Y. [Tokyo Inst. of Tech. (Japan). Faculty of Science; Igashira, M.

1997-03-01

Nuclear reactions induced by keV energy neutrons provide a plenty of informations for studies of both astrophysics and nuclear physics. In this paper we will show our experimental studies of neutron- induced reactions of light nuclei in the keV energy region by means of a pulsed keV neutron beam and high-sensitivity detectors. Also we will discuss astrophysical and nuclear-physical consequences by using the obtained results. (author)

Experimental data on fission and (n,xn) reactions

International Nuclear Information System (INIS)

Belier, G.; Chatillon, A.; Granier, T.; Laborie, J.M.; Laurent, B.; Ledoux, X.; Taieb, J.; Varignon, C.; Bauge, E.; Bersillon, O.; Aupiais, J.; Le Petit, G.; Authier, N.; Casoli, P.

2011-01-01

Investigations on neutron-induced fission of actinides and the deuteron breakup are presented. Neutron-induced fission has been studied for 10 years at the WNR (Weapons Neutron Research) neutron facility of the Los Alamos Neutron Science Center (LANSCE). Thanks to this white neutron source the evolution of the prompt fission neutron energy spectra as a function of the incident neutron energy has been characterized in a single experiment up to 200 MeV incident energy. For some isotopes the prompt neutron multiplicity has been extracted. These experimental results demonstrated the effect on the mean neutron energy of the neutron emission before scission for energies higher than the neutron binding energy. This extensive program ( 235 U and 238 U, 239 Pu, 237 Np and 232 Th were measured) is completed by neutron spectra measurements on the CEA 4 MV accelerator. The D(n,2n) reaction is studied both theoretically and experimentally. The cross-section was calculated for several nucleon-nucleon interactions including the AV18 interaction. It has also been measured on the CEA 7 MV tandem accelerator at incident neutron energies up to 25 MeV. Uncertainties lower than 8% between 5 and 10 MeV were obtained. In particular these experiments have extended the measured domain for cross sections. (authors)

Monodispersepoly[BMA-co-(COPS-I)] Particles by Soap-Free Emulsion Copolymerization and Its Optical Properties as Photonic Crystals.

Science.gov (United States)

Lee, Ki Chang; Choo, Hun Seung

2015-10-01

In order to study the surfactant-free emulsion copolymerization of benzyl methacrylate (BMA) with sodium 1-allyloxy-2-hydroxypropane sulfonate (COPS-I) and the resulting optical properties, a series of experiments was carried out at various reaction conditions such as the changes of BMA concentration, COPS-I concentration, BMA concentration under a fixed COPS-I amount, initiator and divinyl benzene (DVB) concentration. All the latices showed highly monodispersed spherical particles in the size range of 144~435 nm and the respective shiny structural colors from their colloidal photonic crystals. It is found that the changes in such polymerization factors greatly affect the number of particles and particle diameter, polymerization rate, molecular weight, zeta-potential, and refractive indices. The increase of number of particles led to the increased rate of polymerization and zeta-potential of the latices, on the other hand, to the decreased molecular weight. Refractive indices and the reflectivity increased with COPS-I concentration, on the other hand, and decreased with DVB concentration. Especially, refractive indices of the resulting poly[BMA-co-(COPS-I)] colloidal photonic crystals showed much higher values of 1.65~2.21 than that of polystyrene, due to the formation of core-shell shaped morphology. Monodisperse and high refractive index of poly[BMA-co-(COPS-I)] particles prepared in this work could be used for the study in photonic crystals and electrophoretic display.

Investigation of graft copolymerization modification of PTFE surface using microwave plasma

International Nuclear Information System (INIS)

Wen Yunjian; Guan Weishu; Fang Yan; Ying Yongxiang

1995-03-01

Investigation of graft copolymerization modification of PTFE surface with kind of one or another reactive monomers was performed by using non-equilibrium microwave plasma at 2.45 GHz under various operating conditions. Untreated clean samples and grafted samples were examined and analyzed with different surface analytical techniques such as X-Ray Photoelectron Spectroscopy (XPS), Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR) and Scanning Electron Microscopy (SEM). The results showed that the occurrence of noticeable de-fluorination and cross linking on grafted surface, and different polar groups and content of oxygen-containing were introduced into the grafted surface of PTFE. Fibriform hetero-structure layer was also formed. These results confirmed the success of graft and indicated that the hydrophilicity of the grafted surface is excellent and a significant improvement in adhesion characteristics has been achieved. The experiments revealed that the changes in surface properties are correlated closely to the changes in chemical structure, composition and morphology. (8 figs., 1 refs.)

Zwitterionic sulfobetaine-grafted poly(vinylidene fluoride) membrane with highly effective blood compatibility via atmospheric plasma-induced surface copolymerization.

Science.gov (United States)

Chang, Yung; Chang, Wan-Ju; Shih, Yu-Ju; Wei, Ta-Chin; Hsiue, Ging-Ho

2011-04-01

Development of nonfouling membranes to prevent nonspecific protein adsorption and platelet adhesion is critical for many biomedical applications. It is always a challenge to control the surface graft copolymerization of a highly polar monomer from the highly hydrophobic surface of a fluoropolymer membrane. In this work, the blood compatibility of poly(vinylidene fluoride) (PVDF) membranes with surface-grafted electrically neutral zwitterionic poly(sulfobetaine methacrylate) (PSBMA), from atmospheric plasma-induced surface copolymerization, was studied. The effect of surface composition and graft morphology, electrical neutrality, hydrophilicity and hydration capability on blood compatibility of the membranes were determined. Blood compatibility of the zwitterionic PVDF membranes was systematically evaluated by plasma protein adsorption, platelet adhesion, plasma-clotting time, and blood cell hemolysis. It was found that the nonfouling nature and hydration capability of grafted PSBMA polymers can be effectively controlled by regulating the grafting coverage and charge balance of the PSBMA layer on the PVDF membrane surface. Even a slight charge bias in the grafted zwitterionic PSBMA layer can induce electrostatic interactions between proteins and the membrane surfaces, leading to surface protein adsorption, platelet activation, plasma clotting and blood cell hemolysis. Thus, the optimized PSBMA surface graft layer in overall charge neutrality has a high hydration capability and the best antifouling, anticoagulant, and antihemolytic activities when comes into contact with human blood. © 2011 American Chemical Society

Rate coefficients for the reaction of OH radicals with cis-3-hexene: an experimental and theoretical study.

Science.gov (United States)

Barbosa, Thaís da Silva; Peirone, Silvina; Barrera, Javier A; Abrate, Juan P A; Lane, Silvia I; Arbilla, Graciela; Bauerfeldt, Glauco Favilla

2015-04-14

The kinetics of the cis-3-hexene + OH reaction were investigated by an experimental relative rate method and at the density functional theory level. The experimental set-up consisted of a 200 L Teflon bag, operated at atmospheric pressure and 298 K. OH radicals were produced by the photolysis of H2O2 at 254 nm. Relative rate coefficients were determined by comparing the decays of the cis-3-hexene and reference compounds (cyclohexene, 2-buten-1-ol and allyl ether). The mean second-order rate coefficient value found was (6.27 ± 0.66) × 10(-11) cm(3) molecule(-1) s(-1), the uncertainty being estimated by propagation of errors. Theoretical calculations for the addition reaction of OH to cis-3-hexene have also been performed, at the BHandHLYP/aug-cc-pVDZ level, in order to investigate the reaction mechanism, to clarify the experimental observations and to model the reaction kinetics. Different conformations of the reactants, pre-barrier complexes and saddle points were considered in our calculations. The individual rate coefficients, calculated for each conformer of the reactant, at 298 K, using a microcanonical variational transition state method, are 4.19 × 10(-11) and 1.23 × 10(-10) cm(3) molecule(-1) s(-1). The global rate coefficient was estimated from the Boltzmann distribution of the conformers to be 8.10 × 10(-11) cm(3) molecule(-1) s(-1), which is in agreement with the experimental value. Rate coefficients calculated over the temperature range from 200-500 K are also given. Our results suggest that the complex mechanism, explicitly considering different conformations for the stationary points, must be taken into account for a proper description of the reaction kinetics.

Preparation of Syndiotactic Poly(vinyl alcohol)/Poly(vinyl pivalate/vinyl acetate) Microspheres with Radiopacity Using Suspension Copolymerization and Saponification

Science.gov (United States)

Seok Lyoo, Won; Wook Cha, Jin; Young Kwak, Kun; Jae Lee, Young; Yong Jeon, Han; Sik Chung, Yong; Kyun Noh, Seok

2010-06-01

To prepare Poly(vinyl pivalate/vinyl acetate) [P(VPi/VAc)] microspheres with radiopacity, the suspension copolymerization approach in the presence of aqueous radiopaque nanoparticles was used. After, The P(VPi/VAc) microspheres with radiopacity were saponified in heterogeneous system, and then P(VPi/VAc) microspheres without aggregates were converted to s-PVA/P(VPi/VAc) microspheres of skin/core structure through the heterogeneous surface saponification. Radiopacity of microspheres was confirmed with Computed tomography (CT).

Archival and Dissemination of the U.S. and Canadian Experimental Nuclear Reaction Data (EXFOR Project)

Science.gov (United States)

Pritychenko, Boris; Hlavac, Stanislav; Schwerer, Otto; Zerkin, Viktor

2017-09-01

The Exchange Format (EXFOR) or experimental nuclear reaction database and the associated Web interface provide access to the wealth of low- and intermediate-energy nuclear reaction physics data. This resource includes numerical data sets and bibliographical information for more than 22,000 experiments since the beginning of nuclear science. Analysis of the experimental data sets, recovery and archiving will be discussed. Examples of the recent developments of the data renormalization, uploads and inverse reaction calculations for nuclear science and technology applications will be presented. The EXFOR database, updated monthly, provides an essential support for nuclear data evaluation, application development and research activities. It is publicly available at the National Nuclear Data Center website http://www.nndc.bnl.gov/exfor and the International Atomic Energy Agency mirror site http://www-nds.iaea.org/exfor. This work was sponsored in part by the Office of Nuclear Physics, Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-98CH10886 with Brookha ven Science Associates, LLC.

STABILITY OF EMULSIFIER-FREE EMULSION COPOLYMERIZATION OF METHYL METHACRYLATE/ BUTYL ACRYLATE/SODIUM MONO(ETHYL POLYOXYETHYLENE) MALEATE

Institute of Scientific and Technical Information of China (English)

Mao-gen Zhang; Zhi-xue Weng; Zhi-ming Huang; Zu-ren Pan

1999-01-01

A series of new water-soluble bifunctional comonomers having both carboxyl and alkyl polyoxyethylene groups, such as sodium mono(ethyl polyoxyethylene) maleate (ZE series) with various molecular weights of polyoxyethylene ethyl ether, were synthesized and characterized. The effects of the structural factor, the amount and feeding mode of the comonomers, the initiator concentration and polymerization temperature on the stability of emulsifier-free emulsion copolymerization of methyl methacrylate (MMA) and butyl acrylate (BA) in the presence of a small amount of ZE with potassium persulfate as initiator were investigated. Stable, almost monodispersed MMA/BA/ZE emulsifier-free latex particles were prepared.

Computer-Aided Model Based Analysis for Design and Operation of a Copolymerization Process

DEFF Research Database (Denmark)

Lopez-Arenas, Maria Teresa; Sales-Cruz, Alfonso Mauricio; Gani, Rafiqul

2006-01-01

. This will allow analysis of the process behaviour, contribute to a better understanding of the polymerization process, help to avoid unsafe conditions of operation, and to develop operational and optimizing control strategies. In this work, through a computer-aided modeling system ICAS-MoT, two first......The advances in computer science and computational algorithms for process modelling, process simulation, numerical methods and design/synthesis algorithms, makes it advantageous and helpful to employ computer-aided modelling systems and tools for integrated process analysis. This is illustrated......-principles models have been investigated with respect to design and operational issues for solution copolymerization reactors in general, and for the methyl methacrylate/vinyl acetate system in particular. The Model 1 is taken from literature and is commonly used for low conversion region, while the Model 2 has...

Radiation-Induced Copolymerization of Tetrafluoroethylene with {alpha}-Olefine; Copolymersation radiochimique du tetrafluoroethylene avec l'olefine {alpha}; Radiatsionnaya sopolimerizatsiya tetraftorehtilena s {alpha}-olefinom; Copolimerizacion radioquimica del tetrafluoroetileno con la olefina {alpha}

Energy Technology Data Exchange (ETDEWEB)

Tabata, Y.; Ishigure, K.; Shibano, H.; Oshima, K.; Sobue, H. [University of Tokyo, Tokyo (Japan)

1963-11-15

Radiationinduced copolymerizations of olefine monomers with tetrafluoroethylene will be reported. In the cases of ethylene and propylene, the composition of copolymers obtained varies continuously with molar concentration of the components in the monomer mixture, and their melting point varies continuously in the range between the melting points of the composing homopolymers. In the case of isobutene, the composition of copolymer remains constant with the ratio of one to one (alternating copolymer) irrespective of the change in concentration of the components in the monomer mixture and its melting point remains constant (about 200{sup o}C). The copolymers of tetrafluoroethylene/ethylene and tetrafluoroethylene/isobutene show high crystallinity. All the copolymerizations are believed to proceed by a radical mechanism. The case of tetrafluoroethylene/ isobutene seems to be the first observation of alternating copolymer obtained by radical copolymerization. The monomer reactivity ratio of these systems is determined. (author) [French] Les auteurs donnent des indications sur la copolymerisation radioinduite de monomeres d'olefines et du tetrafluoroethylene. Dans le cas de l'ethylene et du propylene, la composition des copolymeres obtenus varie de maniere constante avec la concentration molaire des elements du melange de monomeres, et leur point de fusion varie de maniere constante dans l'intervalle compris entre les points de fusion des homopolymeres qui les composent. Dans le cas de l'isobutene, la composition du copolymere demeure constante dans la proportion de un a un (copolymere alternant), independamment des changements de la concentration des composants du melange de monomeres, et son point de fusion reste constant (200{sup o}C environ). Les copolymeres du tetrafluoroethyleneethylene et du tetrafluoroethylene-isobutene presentent un degre eleve de cristallinite. Les auteurs arrivent a la conclusion que toutes les copolymerisations se font par effet des radicaux

Experimental Study on Reaction Characteristics of PTFE/Ti/W Energetic Materials under Explosive Loading

Directory of Open Access Journals (Sweden)

Yan Li

2016-11-01

Full Text Available Metal/fluoropolymer composites represent a new category of energetic structural materials that release energy through exothermic chemical reactions initiated under shock loading conditions. This paper describes an experiment designed to study the reaction characteristics of energetic materials with low porosity under explosive loading. Three PTFE (polytetrafluoroethylene/Ti/W mixtures with different W contents are processed through pressing and sintering. An inert PTFE/W mixture without reactive Ti particles is also prepared to serve as a reference. Shock-induced chemical reactions are recorded by high-speed video through a narrow observation window. Related shock parameters are calculated based on experimental data, and differences in energy release are discussed. The results show that the reaction propagation of PTFE/Ti/W energetic materials with low porosity under explosive loading is not self-sustained. As propagation distance increases, the energy release gradually decreases. In addition, reaction failure distance in PTFE/Ti/W composites is inversely proportional to the W content. Porosity increased the failure distance due to higher shock temperature.

The experimental nuclear reaction data (EXFOR): Extended computer database and Web retrieval system

Science.gov (United States)

Zerkin, V. V.; Pritychenko, B.

2018-04-01

The EXchange FORmat (EXFOR) experimental nuclear reaction database and the associated Web interface provide access to the wealth of low- and intermediate-energy nuclear reaction physics data. This resource is based on numerical data sets and bibliographical information of ∼22,000 experiments since the beginning of nuclear science. The principles of the computer database organization, its extended contents and Web applications development are described. New capabilities for the data sets uploads, renormalization, covariance matrix, and inverse reaction calculations are presented. The EXFOR database, updated monthly, provides an essential support for nuclear data evaluation, application development, and research activities. It is publicly available at the websites of the International Atomic Energy Agency Nuclear Data Section, http://www-nds.iaea.org/exfor, the U.S. National Nuclear Data Center, http://www.nndc.bnl.gov/exfor, and the mirror sites in China, India and Russian Federation.

Metallocene-catalyzed ethylene−α-olefin isomeric copolymerization: A perspective from hydrodynamic boundary layer mass transfer and design of MAO anion

KAUST Repository

Adamu, Sagir

2015-11-28

This study reports a novel conceptual framework that can be easily experimented to evaluate the effects of hydrodynamic boundary layer mass transfer, methylaluminoxane (MAO) anion design, and comonomer steric hindrance on metallocene-catalyzed ethylene polymerization. This approach was illustrated by conducting homo- and isomeric copolymerization of ethylene with 1-hexene and 4-methyl-1-pentene in the presence of bis(n-butylcyclopentadienyl) zirconium dichloride (nBuCp)2ZrCl2, using (i) MAO anion 1 (unsupported [MAOCl2]−) and pseudo-homogeneous reference polymerization, and (ii) MAO anion 2 (supported Si−O−[MAOCl2]−) and in-situ heterogeneous polymerization. The measured polymer morphology, catalyst productivity, molecular weight distribution, and inter-chain composition distribution were related to the locus of polymerization, comonomer effect, in-situ chain transfer process, and micromixing effect, respectively. The peak melting and crystallization temperatures and %crystallinity were mathematically correlated to the parameters of microstructural composition distributions, melt fractionation temperatures, and average lamellar thickness. These relations showed to be insightful. The comonomer-induced enchainment defects and the eventual partial disruption of the crystal lattice were successfully modeled using Flory and Gibbs–Thompson equations. The present methodology can also be applied to study ethylene−α-olefin copolymerization, performed using MAO-activated non-metallocene precatalysts.

Experimental determination of nuclear reaction rates (n,γ) by the gamma-rays capture spectrometry technique

International Nuclear Information System (INIS)

Lucatero, M.A.

1976-01-01

The technique of the gamma-rays capture spectrometry was used in the experimental determination of nuclear reaction rates of the type (n,γ). This technique consists in the incidence of a thermal neutrons collimated beam upon a sample, detecting the capture spectrum of gamma rays emitted at a solid fixed angle. In the determination of the efficiency curve intrinsic to the detection electronic system the reactions 199 Hg(n,γ) 200 Hg, 56 Fe(n,γ) 57 Fe and 63 Cu(n,γ) 64 Cu were used with the energy of the gamma rays capture of 5.976, 7.635 and 7.915 Mev respectively, through the irradiation of standard samples of Hg(175.3g), Fe(110.4g) and Cu(108.5g) of cylindrical geometry the two former and parallelepiped the latter. The problem concerning the corrections due to the thermal neutrons flux depression, the gammas auto-attenuation, and the geometric factor due to the cylindrical and parallelepiped geometry are involved in the data process. The experimental determination of the reaction 35 Cl(n,γ) 36 Cl rate was made through the observation of the gamma caputre of 6.111 Mev when a sample of CaCl 2 of cylindrical geometry was irradiated. This rate can be favorably compared with the reaction rate determined theoretically. (author)

Examination and experimental constraints of the stellar reaction rate factor N-A of the Ne-18(alpha, p)Na-21 reaction at temperatures of x-ray bursts

NARCIS (Netherlands)

Matic, A.; Mohr, P.

2013-01-01

The Ne-18(alpha, p)Na-21 reaction is one key for the breakout from the hot CNO cycles to the rp-process. Recent papers have provided reaction rate factors N-A which are discrepant by at least one order of magnitude. The compatibility of the latest experimental results is tested, and a partial

Coordination behavior of bis-phenolate saturated and unsaturated N-heterocyclic carbene ligands to zirconium: reactivity and activity in the copolymerization of cyclohexene oxide with CO2.

Science.gov (United States)

Lalrempuia, Ralte; Breivik, Frida; Törnroos, Karl W; Le Roux, Erwan

2017-06-27

controlled manner (M w /M n ≈ 1.3-1.8). In contrast, the isolated homoleptic, zwitterionic and bimetallic zirconium species were found to be inactive under similar reaction conditions. Although the activity found for NHC-Zr(iv) complexes is nearly of the same order of magnitude as that of the NHC-Ti(iv) analogues, these results are the first examples of tetravalent zirconium complexes achieving high selectivity (99% in PCHC) in the catalyzed copolymerization of CHO with CO 2 .

A study on radiation-induced graft copolymerization of monomer onto natural silk fabric

International Nuclear Information System (INIS)

Xiang Zhengyu; Wan Dairong; He Qian

1995-02-01

In order to improve the properties of natural silk fabric, the mechanism and method of the radiation induced graft copolymerization of monomers onto natural silk fabric were studied. Three monomers, acrylamide, methylacrylamide and hydroxymethyl acrylamide, were selected for grafting test according to requirements of graft processing. The processing conditions of monomer infusion were studied. The properties of grafted samples were measured. The results are as follows: the rate of weight increasing is 10%∼29%; the rate of thickness increasing is 5%∼20%; the abrupt elasticity rose by 30%; the retarded elasticity rose by 12%; wet elasticity rose by 40%; and the brightness of colour and lustre were improved. It is concluded that while the radiation grafted silk kept its natural characteristics, other properties were improved. It became even chubby and thicker. (4 refs., 3 figs., 3 tabs.)

Radiation reaction studies in an all-optical set-up: experimental limitations

Science.gov (United States)

Samarin, G. M.; Zepf, M.; Sarri, G.

2018-06-01

The recent development of ultra-high intensity laser facilities is finally opening up the possibility of studying high-field quantum electrodynamics in the laboratory. Arguably, one of the central phenomena in this area is that of quantum radiation reaction experienced by an ultra-relativistic electron beam as it propagates through the tight focus of a laser beam. In this paper, we discuss the major experimental challenges that are to be faced in order to extract meaningful and quantitative information from this class of experiments using existing and near-term laser facilities.

Experimental setup and procedure for the measurement of the {sup 7}Be(n,α)α reaction at n-TOF

Energy Technology Data Exchange (ETDEWEB)

Cosentino, L. [INFN Laboratori Nazionali del Sud, Catania (Italy); Musumarra, A. [INFN Laboratori Nazionali del Sud, Catania (Italy); Dipartimento di Fisica e Astronomia DFA, Università di Catania (Italy); Barbagallo, M. [INFN Sezione di Bari (Italy); Pappalardo, A. [INFN Laboratori Nazionali del Sud, Catania (Italy); Colonna, N.; Damone, L. [INFN Sezione di Bari (Italy); Piscopo, M. [INFN Laboratori Nazionali del Sud, Catania (Italy); Finocchiaro, P., E-mail: FINOCCHIARO@LNS.INFN.IT [INFN Laboratori Nazionali del Sud, Catania (Italy); Maugeri, E.; Heinitz, S.; Schumann, D.; Dressler, R.; Kivel, N. [Paul Scherrer Institut, Nuclear Energy and Safety Research Department, 5232 Villigen (Switzerland); Aberle, O. [CERN, Geneva (Switzerland); Andrzejewski, J. [Uniwersytet Łódzki, Lodz (Poland); Audouin, L. [Institut de Physique Nucléaire, CNRS-IN2P3, Univ. Paris-Sud, Université Paris-Saclay, 91406 Orsay Cedex (France); Ayranov, M. [European Commission, DG-Energy (Luxembourg); Bacak, M. [Atominstitut der Österreichischen Universitäten, Technische Universität Wien (Austria); Barros, S. [C2TN-Instituto Superior Tecníco, Universidade de Lisboa (Portugal); Balibrea-Correa, J. [Centro de Investigaciones Energeticas Medioambientales y Tecnológicas (CIEMAT), Madrid (Spain); and others

2016-09-11

The newly built second experimental area EAR2 of the n-TOF spallation neutron source at CERN allows to perform (n, charged particles) experiments on short-lived highly radioactive targets. This paper describes a detection apparatus and the experimental procedure for the determination of the cross-section of the {sup 7}Be(n,α)α reaction, which represents one of the focal points toward the solution of the cosmological Lithium abundance problem, and whose only measurement, at thermal energy, dates back to 1963. The apparently unsurmountable experimental difficulties stemming from the huge {sup 7}Be γ-activity, along with the lack of a suitable neutron beam facility, had so far prevented further measurements. The detection system is subject to considerable radiation damage, but is capable of disentangling the rare reaction signals from the very high background. This newly developed setup could likely be useful also to study other challenging reactions requiring the detectors to be installed directly in the neutron beam.

Design of an experimental device dedicated to the measurement of spallation reactions; Mise au point d'un dispositif experimental pour des mesures exclusives des reactions de spallation

Energy Technology Data Exchange (ETDEWEB)

Lafriakh, A

2005-12-15

Spallation mechanisms are not yet completely understood, especially because of the difficulty of experimentally disentangling the effects of the different steps of the reaction. In order to understand these mechanisms, we have developed a new experimental device able to perform inclusive measurements. We propose a detection system based on a combination of ionization chambers and proportional counters and on a wall of plastic scintillators to measure light charged particles. In particular the detection of light charged particles is described in detail. In order to validate our device, we have compared our preliminary results obtained on the Fe{sup 56} + p system at 1 GeV/u with inclusive measurements previously obtained at the FRS spectrometer of the GSI facility. A comparison of charge differential cross section shows reasonable agreement. However, our new device allowed extension of those measurements down to Z = 1 and Z = 2. These cross sections are important for material damage studies. Taking into account our error brackets, the evolution of mean longitudinal velocities with respect to residue masses is comparable to that obtained at the FRS. These first results, although preliminary, allow us to validate our experimental device. It is now possible to exploit the strong points of our exclusive measurements, namely correlations between different measured observables. Finally, experimental problems encountered will be taken into account in the future experimental programs, in order to ensure the best measurements conditions.

Spin-selective recombination reactions of radical pairs: Experimental test of validity of reaction operators

Energy Technology Data Exchange (ETDEWEB)

Maeda, Kiminori [Department of Chemistry, University of Oxford, Centre for Advanced Electron Spin Resonance, Inorganic Chemistry Laboratory, Oxford (United Kingdom); Liddell, Paul; Gust, Devens [Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona, 85287-1604 (United States); Hore, P. J. [Department of Chemistry, University of Oxford, Physical and Theoretical Chemistry Laboratory, Oxford (United Kingdom)

2013-12-21

Spin-selective reactions of radical pairs are conventionally modelled using an approach that dates back to the 1970s [R. Haberkorn, Mol. Phys. 32, 1491 (1976)]. An alternative approach based on the theory of quantum measurements has recently been suggested [J. A. Jones and P. J. Hore, Chem. Phys. Lett. 488, 90 (2010)]. We present here the first experimental attempt to discriminate between the two models. Pulsed electron paramagnetic resonance spectroscopy has been used to investigate intramolecular electron transfer in the radical pair form of a carotenoid-porphyrin-fullerene molecular triad. The rate of spin-spin relaxation of the fullerene radical in the triad was found to be inconsistent with the quantum measurement description of the spin-selective kinetics, and in accord with the conventional model when combined with spin-dephasing caused by rotational modulation of the anisotropic g-tensor of the fullerene radical.

Experimental deformation of a mafic rock - interplay between fracturing, reaction and viscous deformation

Science.gov (United States)

Marti, Sina; Stünitz, Holger; Heilbronner, Renée; Plümper, Oliver; Drury, Martyn

2016-04-01

Deformation experiments were performed on natural Maryland Diabase (˜ 55% Plg, 42% Px, 3% accessories, 0.18 wt.-% H2O added) in a Griggs-type deformation apparatus in order to explore the brittle-viscous transition and the interplay between deformation and mineral reactions. Shear experiments at strain rates of ˜ 2e-5 /s are performed, at T=600, 700 and 800°C and confining pressures Pc=1.0 and 1.5 GPa. Deformation localizes in all experiments. Below 700°C, the microstructure is dominated by brittle deformation with a foliation formed by cataclastic flow and high strain accommodated along 3-5 major ultracataclasite shear bands. At 700°C, the bulk of the material still exhibits abundant microfractures, however, deformation localizes into an anastomosing network of shear bands (SB) formed from a fine-grained (<< 1 μm) mixture of newly formed Plg and Amph. These reaction products occur almost exclusively along syn-kinematic structures such as fractures and SB. Experiments at 800°C show extensive mineral reactions, with the main reaction products Amph+Plg (+Zo). Deformation is localized in broad C' and C SB formed by a fine-grained (0.1 - 0.8 μm) mixture of Plg+Amph (+Zo). The onset of mineral reactions in the 700°C experiments shows that reaction kinetics and diffusional mass transport are fast enough to keep up with the short experimental timescales. While in the 700°C experiments brittle processes kinematically contribute to deformation, fracturing is largely absent at 800°C. Diffusive mass transfer dominates. The very small grain size within SB favours a grain size sensitive deformation mechanism. Due to the presence of water (and relatively high supported stresses), dissolution-precipitation creep is interpreted to be the dominant strain accommodating mechanism. From the change of Amph coronas around Px clasts with strain, we can determine that Amph is re-dissolved at high stress sites while growing in low stress sites, showing the ability of Amph to

Recent experimental results in sub- and near-barrier heavy-ion fusion reactions

Energy Technology Data Exchange (ETDEWEB)

Montagnoli, Giovanna [Dipartimento di Fisica e Astronomia, Universita di Padova (Italy); INFN Sezione di Padova (Italy); Stefanini, Alberto M. [INFN, Laboratori Nazionali di Legnaro, Legnaro (Padova) (Italy)

2017-08-15

Recent advances obtained in the field of near and sub-barrier heavy-ion fusion reactions are reviewed. Emphasis is given to the results obtained in the last decade, and focus is mainly on the experimental work performed concerning the influence of transfer channels on fusion cross sections and the hindrance phenomenon far below the barrier. Indeed, early data of sub-barrier fusion taught us that cross sections may strongly depend on the low-energy collective modes of the colliding nuclei, and, possibly, on couplings to transfer channels. The coupled-channels (CC) model has been quite successful in the interpretation of the experimental evidences. Fusion barrier distributions often yield the fingerprint of the relevant coupled channels. Recent results obtained by using radioactive beams are reported. At deep sub-barrier energies, the slope of the excitation function in a semi-logarithmic plot keeps increasing in many cases and standard CC calculations overpredict the cross sections. This was named a hindrance phenomenon, and its physical origin is still a matter of debate. Recent theoretical developments suggest that this effect, at least partially, may be a consequence of the Pauli exclusion principle. The hindrance may have far-reaching consequences in astrophysics where fusion of light systems determines stellar evolution during the carbon and oxygen burning stages, and yields important information for exotic reactions that take place in the inner crust of accreting neutron stars. (orig.)

Experimental and numerical analysis of the combustor for a cogeneration system based on the aluminum/water reaction

International Nuclear Information System (INIS)

Milani, Massimo; Montorsi, Luca; Paltrinieri, Fabrizio; Stefani, Matteo

2014-01-01

Highlights: • Aluminum reaction with water is studied as a technology for hydrogen production. • A test rig is developed for the analysis of aluminum/water reaction. • The system is the core component of a cogeneration plant for hydrogen/power production. • The interaction of liquid aluminum jet and water steam stream is investigated. • The main capabilities of the injection system are assessed. - Abstract: The paper focuses on the design of the experimental apparatus aimed at analyzing the performance of the combustion chamber of a cogeneration system based on the reaction of liquid aluminum and water steam. The cogeneration system exploits the heat released by the oxidation of aluminum with water for super-heating the vapor of a steam cycle and simultaneously producing hydrogen. The only by-product is alumina, which in a closed loop can be recycled back and transformed again into aluminum. Therefore, aluminum is used as an energy carrier to transport the energy from the alumina reduction plant to the location of the proposed system. The water is also used in a closed loop since the amount of water produced employing the hydrogen obtained by the proposed system corresponds to the oxidizing water for the Al/H 2 O reaction. This study investigates the combustor where the liquid aluminum–steam reaction takes place. In particular, the design of the combustion chamber and the interaction between the liquid aluminum jet and the water steam flow are evaluated using a numerical and an experimental approach. The test rig is specifically designed for the analysis of the liquid aluminum injection in a slightly super-heated steam stream. The first experiments are carried out to verify the correct behavior of the test rig. Thermography is employed to qualitatively assess the steam entrainment of the liquid aluminum jet. Finally, the experimental measurements are compared with the multi-dimension multi-phase flow simulations in order to estimate the influence of

Reactions to ingroup and outgroup deviants: an experimental group paradigm for black sheep effect.

Directory of Open Access Journals (Sweden)

Marika Rullo

Full Text Available In the classic black sheep effect (BSE an ingroup deviant member is usually evaluated more negatively than the corresponding outgroup deviant. This effect is usually obtained by using scenarios and asking people to imagine the situation as vividly as possible. The present study proposes a new method to investigate the BSE by considering the behavioral and physiological reactions to unfair behavior (aggressive game behavior in a realistic experimental group-setting. The study involved 52 university students in a minimal group setting who performed a modified version of the competitive reaction time (CRT task adapted to be played in groups of four people. The classic BSE was replicated for evaluation but not for the behavioral reactions (retaliate to aggression to deviants. More interestingly, a negative relationship emerged in the ingroup deviant condition between the level of behavioral derogation and the systolic blood pressure level.

Experimental investigations of different steel resistances in the sodium-steam reaction zone

International Nuclear Information System (INIS)

Mazanov, A.S.; Kulpin, B.V.; Petukhov, V.P.; Ledovskikh, N.M.

1975-01-01

The results are stated on the experimental investigations of IX2M, IXI8HIOT, OXI2H2M and Sanikro-31 steel resistance in the sodium-steam reaction zone. A target in the form of a pipe was used in the experiments within which the excessive pressure of 95 atm. was produced with an inert gas. Steam was supplied through the nozzle to the sodium tank in which there was a movable target unit. The dependence of time-to failure and failure rate on the distance of the nozzle and target wall thickness was estimated for these steels. It was shown that the resistance of Sanikro-31 in the sodium steam reaction zone was 2.5, 3.5 and 6 times that of IXI8HIOT, OXI2H2M, IX2M steels, respectively. The failure curves were obtained on thin targets for two steels (author)

Experimental study of the (n,alpha) reaction on a set of light nuclei

International Nuclear Information System (INIS)

Khryachkov, V.A.; Bondarenko, I.P.; Kuzminov, B.D.; Semenova, N.N.; Sergachev, A.I.; Giorginis, G.

2011-01-01

An experimental setup based on an ionization chamber with Frisch grid and waveform digitizer was used for (n,α) cross-section measurements. The use of digital signal processing has allowed us to select a gaseous cell inside the sensitive area of the ionisation chamber with high accuracy. This kind of approach provides a powerful method to suppress background from detector components and parasitic reactions on the working gas. The new method is especially interesting for the study of reactions on elements for which solid target preparation is difficult (e.g. noble gases). Additionally it has the advantage of an accurate determination of the number of nonradioactive nuclei in the selected gas cell. In the present experiments a set of working gases was used, which contained admixtures of nitrogen, oxygen, neon, argon and boron. Fission of "2"3"8U was used as neutron flux monitor. The cross-section of the (n,α) reaction for "1"6O, "1"4N, "2"0Ne, "3"6Ar, "4"0Ar and the branching ratio α_0/α_1 of the "1"0B(n,α_0) to "1"0B(n,α_1) reactions were measured for neutron energies between 1.5 and 7 MeV. (authors)

Bio-waste corn-cob cellulose supported poly(hydroxamic acid) copper complex for Huisgen reaction: Waste to wealth approach.

Science.gov (United States)

Mandal, Bablu Hira; Rahman, Md Lutfor; Yusoff, Mashitah Mohd; Chong, Kwok Feng; Sarkar, Shaheen M

2017-01-20

Corn-cob cellulose supported poly(hydroxamic acid) Cu(II) complex was prepared by the surface modification of waste corn-cob cellulose through graft copolymerization and subsequent hydroximation. The complex was characterized by IR, UV, FESEM, TEM, XPS, EDX and ICP-AES analyses. The complex has been found to be an efficient catalyst for 1,3-dipolar Huisgen cycloaddition (CuAAC) of aryl/alkyl azides with a variety of alkynes as well as one-pot three-components reaction in the presence of sodium ascorbate to give the corresponding cycloaddition products in up to 96% yield and high turn over number (TON 18,600) and turn over frequency (TOF 930h -1 ) were achieved. The complex was easy to recover from the reaction mixture and reused six times without significant loss of its catalytic activity. Copyright © 2016 Elsevier Ltd. All rights reserved.

Estudio de copolimerización injerto del acrilato de butilo sobre almidón empleando sistema iniciador redox

Directory of Open Access Journals (Sweden)

Alfredo Carlos Martinez-Arellano

2014-06-01

Full Text Available The mixture of synthetic and natural materials yields a material with improved physical-chemical properties. One way of obtaining this kind of material is through graft copolymerization. Some natural materials have been used in graft copolymerization with synthetic monomers. In this work, graft copolymerization of butyl acrylate (BA onto starch using a redox initiator system was carried out. The graft yield was evaluated for different reaction conditions. The graft copolymer was characterized by infrared spectroscopy, thermal analysis and scanning electron microscopy (SEM.

Design of an experimental device dedicated to the measurement of spallation reactions; Mise au point d'un dispositif experimental pour des mesures exclusives des reactions de spallation

Energy Technology Data Exchange (ETDEWEB)

Lafriakh, A

2005-12-15

Spallation mechanisms are not yet completely understood, especially because of the difficulty of experimentally disentangling the effects of the different steps of the reaction. In order to understand these mechanisms, we have developed a new experimental device able to perform inclusive measurements. We propose a detection system based on a combination of ionization chambers and proportional counters and on a wall of plastic scintillators to measure light charged particles. In particular the detection of light charged particles is described in detail. In order to validate our device, we have compared our preliminary results obtained on the Fe{sup 56} + p system at 1 GeV/u with inclusive measurements previously obtained at the FRS spectrometer of the GSI facility. A comparison of charge differential cross section shows reasonable agreement. However, our new device allowed extension of those measurements down to Z = 1 and Z = 2. These cross sections are important for material damage studies. Taking into account our error brackets, the evolution of mean longitudinal velocities with respect to residue masses is comparable to that obtained at the FRS. These first results, although preliminary, allow us to validate our experimental device. It is now possible to exploit the strong points of our exclusive measurements, namely correlations between different measured observables. Finally, experimental problems encountered will be taken into account in the future experimental programs, in order to ensure the best measurements conditions.

Copolymerization of Ethylene Induced by Cobalt-60 Gamma Radiation; Copolymerisation de l'ethylene induite par des rayons gamma du cobalt-60; Sopolimerizatsiya ehtilena pod dejstviem gamma-izlucheniya ot istochnika ks'yali-60; Copolimerizacion del etileno inducida por las radiaciones gamma del cobalto-60

Energy Technology Data Exchange (ETDEWEB)

Steinberg, M.; Colombo, P. [Brookhaven National Laboratory, Long Island, NY (United States)

1963-11-15

The gamma radiation initiated copolymerization of ethylene with a number of different monomers was studied at 20{sup o}C and initial pressures up to 680 atm. The experiments were conducted statically in two-phase systems with the exception of the ethylene-carbon monoxide system. Isolation of the copolymers was effected by solvent extraction and fractional precipitation techniques. Infra-red spectroscopy was used for identification. The composition was determined by elemental analysis. A partial evaluation of some of the reaction products including crystalline melting points, densities, solubility characteristics, and molecular weights are given. Evidence of ethylene copolymerization was established with each of the following monomers: styrene, methyl methacrylate, vinyl acetate, acrylonitrile, allyl acetate, isobutylene, chlorotrifluoroethylene, trans 2-butene, methyl acrylate, isoprene, propylene, vinyl chloride, 1-butene, cis 2-butene, carbon monoxide, vinyl pyrrolidone, methyl vinyl ketone, and divinyl benzene. The experimental data obtained in the study of the ethylene-carbon monoxide system were found to obey a linear form of the copolymer composition equation. The ratio of specific rate constants for carbon monoxide and ethylene ({alpha}) was found to have a value of 22.0, indicating that carbon monoxide as a monomer, is activated to the extent that it adds 22 times as fast as an ethylene monomer to an ethylene free-radical chain end. Explosive decomposition was observed to occur during irradiation of ethylene arid chlorotrifluoroethylene under certain irradiation conditions. There is an indication that a threshold radiation intensity exists which induces this violent reaction. The unique advantage of cobalt-60 gamma radiation is that it can be used to induce and control ethylene copolymerization reactions at low temperatures. (author) [French] La copolymerisation de l'ethylene avec divers monomeres provoquee avec des rayons gamma a ete etudiee a 20{sup o

Halloysite nanotubes grafted hyperbranched (co)polymers via surface-initiated self-condensing vinyl (co)polymerization

International Nuclear Information System (INIS)

Mu Bin; Zhao Mingfei; Liu Peng

2008-01-01

Halloysite nanotubes (HNTs) grafted hyperbranched polymers were prepared by the self-condensing vinyl polymerization (SCVP) of 2-((bromoacetyl)oxy)ethyl acrylate (BAEA) and the self-condensing vinyl copolymerization of n-butyl acrylate (BA) and BAEA with BAEA as inimer (AB*) respectively, from the surfaces of the 2-bromoisobutyric acid modified halloysite nanotubes (HNTs-Br) via atom transfer radical polymerization (ATRP) technique. The halloysite nanotubes grafted hyperbranched polymer (HNTs-HP) and the halloysite nanotubes grafted hyperbranched copolymer (HNTs-HCP) were characterized by elemental analysis (EA), Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and transmission electron microscope (TEM). The grafted hyperbranched polymers were characterized with Nuclear magnetic resonance (NMR) and the molecular ratio between the inimer AB* and BA in the grafted hyperbranched copolymers was found to be 3:2, calculated from the TGA and EA results

Halloysite nanotubes grafted hyperbranched (co)polymers via surface-initiated self-condensing vinyl (co)polymerization

Energy Technology Data Exchange (ETDEWEB)

Mu Bin; Zhao Mingfei; Liu Peng [Lanzhou University, State Key Laboratory of Applied Organic Chemistry and Institute of Polymer Science and Engineering, College of Chemistry and Chemical Engineering (China)], E-mail: pliu@lzu.edu.cn

2008-05-15

Halloysite nanotubes (HNTs) grafted hyperbranched polymers were prepared by the self-condensing vinyl polymerization (SCVP) of 2-((bromoacetyl)oxy)ethyl acrylate (BAEA) and the self-condensing vinyl copolymerization of n-butyl acrylate (BA) and BAEA with BAEA as inimer (AB*) respectively, from the surfaces of the 2-bromoisobutyric acid modified halloysite nanotubes (HNTs-Br) via atom transfer radical polymerization (ATRP) technique. The halloysite nanotubes grafted hyperbranched polymer (HNTs-HP) and the halloysite nanotubes grafted hyperbranched copolymer (HNTs-HCP) were characterized by elemental analysis (EA), Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and transmission electron microscope (TEM). The grafted hyperbranched polymers were characterized with Nuclear magnetic resonance (NMR) and the molecular ratio between the inimer AB* and BA in the grafted hyperbranched copolymers was found to be 3:2, calculated from the TGA and EA results.

The chemical modification and characterization of polypropylene membrane with environment response by in-situ chlorinating graft copolymerization

Science.gov (United States)

Zhang, Yue; Liu, Jiankai; Hu, Wenjie; Feng, Ying; Zhao, Jiruo

2017-08-01

In this study, a novel chemical surface modification method of polyolefin membranes is applied following the in-situ chlorinating graft copolymerization (ISCGC). Polypropylene (PP)/methyl methacrylate (MMA) system was used as an example. A unique structure was formed by the modification process on the original membrane surface and the product exhibited an environmental response. Chlorine free radicals were generated using ultraviolet and heat and were used to capture the hydrogen in the polymer chains on the substrate surface. The formed macromolecular radicals could react with MMA over 2 h to achieve a high coverage ratio polymer on the PP membrane surface. The graft copolymers were characterized using FTIR, 1H-NMR, DSC, and XPS, which all proved the feasibility of chemically modifying the PP membrane surface by ISCGC. The surface morphology of the grafted PP membrane was characterized using SEM and AFM. The results showed that the grafted product presents a uniform, neat, and dense mastoid structure with an average thickness of 4.44 μm, which was expected to be similar to the brush-like surface structure. The contact angle and AFM tests indicated that the product surface is responsive to solvent and pH. The experimental results showed that the PP membrane surface structure can be reconstructed using ISCGC, a method that can be used for environment-responsive polymer materials. Moreover, the product has the characteristics of polymer interfacial brush.

Experimental method for investigating γd→pn photodisintegration reaction on the linearly polarized photon beam of the Erevan synchrotron

International Nuclear Information System (INIS)

Agababyan, K.Sh.; Adamyan, F.V.; Ajrapetyan, A.V.

1985-01-01

The experimental method for measuring the asymmetry of the γd → pn photodisintegration reaction on the linearly polarized photon beam of the Erevan synchrotron is described. The results of Monte Carlo calculations, the calibration of apparatus, the procedure of measurements and experimental data processing are repored

Preparation of metal ion exchange resin by radiation-induced graft copolymerization

International Nuclear Information System (INIS)

Nakase, Yoshiaki; Akasaka, Nobuhiro.

1982-06-01

Radiation-induced graft copolymerization of 2-acrylamide-2-methyl propane sulfonic acid (AMPS) onto polyvinylchloride (PVC) and polyvinylidene chloride resin (PVD) was investigated in the water-acetone system and their adsorptive activities to metal ion were also examined. In the case of PVC, the degree of grafting increased with the increase of acetone content, but the adsorptive activity to metal ions (mainly lithic ion) became maximum in the system with water/acetone of 2/3. Grafted PVC prepared at about 35 0 C and at a higher concentration of AMPS showed higher adsorption activity than the other cases. In the case of PVD, a similar result was obtained with the case of PVC except the temperature dependence and effect of swelling agent. Polymerizations at temperatures of 35 and 50 0 C showed no effect on the degree of grafting, and the usage of a swelling agent was quite effective to the adsorptive activity. Glass transition temperature of the grafted copolymer was the same as that of original polymer, and their thermal stability was confirmed up to the temperature at which homopolymer of AMPS decomposed, about 180 0 C. (author)

Preparation of polymer electrolyte membranes for lithium batteries by radiation-induced graft copolymerization

Energy Technology Data Exchange (ETDEWEB)

Nasef, Mohamed Mahmoud [Business and Advanced Technology Centre, Universiti Teknologi Malaysia, Jalan Semarak, 54100 Kuala Lumpur (Malaysia); Suppiah, Raja Rajeswary [Chemical Engineering Program, Universiti Teknologi Petronas, Bandar Seri Iskandar, 37150 Tronoh, Perak (Malaysia); Dahlan, Khairul Zaman Mohd [Malaysian Institute for Nuclear Technology Research, Bangi, 43000 Kajang (Malaysia)

2004-07-30

Polymer electrolyte membranes with different degrees of grafting were prepared by radiation-induced graft copolymerization of styrene monomer onto poly(vinylidene fluoride) (PVDF) films and subsequent chemical activation with liquid electrolyte consisting of lithium hexafluorophosphate (LiPF{sub 6}) in a mixture of ethylene carbonate/diethylene carbonate (EC/DEC). The chemical changes in the PVDF films after styrene grafting and subsequent chemical activation were monitored by FTIR spectroscopic analysis and the crystallinity was evaluated using differential scanning calorimetric (DSC) analysis. The swelling in electrolyte solution (electrolyte uptake) and the ionic conductivity of the membranes were determined at various degrees of grafting. The conductivity of the membranes was found to increase with the increase in the degree of grafting and reached a magnitude of 10{sup -3} S/cm at a degree of grafting of 50%. The results of this work suggest that radiation-induced graft polymerization provides an alternative method to substitute blending in preparation of polymer electrolyte membranes for application in lithium batteries.

Study on immobilized yeast cells with hydrophilic polymer carrier by radiation-induced copolymerization

International Nuclear Information System (INIS)

Li Zhengkui; Zhang Bosen

1993-01-01

Various kinds of monomers 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), hydroxypropyl methacrylate (HPMA) and methoxy polyethylene glycol methylacrylate (M-23G) are copolymerized by radiation technique at low temperature (-78 degree C) and several kinds of copolymer carriers were obtained. Yeast cells are immobilized through adhesion and multiplication of yeast cells themselves on these carriers. The ethanol productivity of immobilized yeast cells with these carriers was related to the monomer composition and water content of copolymer carriers and the optimum monomer composition was 20%:10% in poly (HEA-M23G). In this case, the ethanol productivity of immobilized yeast cells was 26 mg/(ml · h), which was 4 times as high as that of free cells. Effect of adding crosslinking reagent (4G) in lower monomer composition of poly(HEA-M23G) on the ethanol productivity of immobilized cells was better than that in higher one in this work

Comparison of experimental and theoretical reaction rail currents, rail voltages, and airgap fields for the linear induction motor research vehicle

Science.gov (United States)

Elliott, D. G.

1977-01-01

Measurements of reaction rail currents, reaction rail voltages, and airgap magnetic fields in tests of the Linear Induction Motor Research Vehicle (LIMRV) were compared with theoretical calculations from the mesh/matrix theory. It was found that the rail currents and magnetic fields predicted by the theory are within 20 percent of the measured currents and fields at most motor locations in most of the runs, but differ by as much as a factor of two in some cases. The most consistent difference is a higher experimental than theoretical magnetic field near the entrance of the motor and a lower experimental than theoretical magnetic field near the exit. The observed differences between the theoretical and experimental magnetic fields and currents do not account for the differences of as much as 26 percent between the theoretical and experimental thrusts.

Combined steam and carbon dioxide reforming of methane and side reactions: Thermodynamic equilibrium analysis and experimental application

International Nuclear Information System (INIS)

Jang, Won-Jun; Jeong, Dae-Woon; Shim, Jae-Oh; Kim, Hak-Min; Roh, Hyun-Seog; Son, In Hyuk; Lee, Seung Jae

2016-01-01

Highlights: • Selected variables have a significant influence on yields of synthesis gas. • (CO_2 + H_2O)/CH_4 affects the temperature which can achieve the maximum conversion. • Coke is formed at low temperatures even with excess oxidizing agent. • The occurrence of RWGS becomes critical in real chemical reactions. • Equilibrium conversions are maintained for 500 h without detectable deactivation. - Abstract: Thermodynamic equilibrium analysis of the combined steam and carbon dioxide reforming of methane (CSCRM) and side reactions was performed using total Gibbs free energy minimization. The effects of (CO_2 + H_2O)/CH_4 ratio (0.9–2.9), CO_2:H_2O ratio (3:1–1:3), and temperature (500–1000 °C) on the equilibrium conversions, yields, coke yield, and H_2/CO ratio were investigated. A (CO_2 + H_2O)/CH_4 ratio greater than 1.2, a CO_2:H_2O ratio of 1:2.1, and a temperature of at least 850 °C are preferable reaction conditions for the synthesis gas preparation in the gas to liquid process. Simulated conditions were applied to the CSCRM reaction and the experimental data were compared with the thermodynamic equilibrium results. The thermodynamic equilibrium results were mostly consistent with the experimental data, but the reverse water gas shift reaction rapidly occurred in the real chemical reaction and under excess oxidizing agent conditions. In addition, a long-term stability test (under simulated conditions) showed that the equilibrium conversion was maintained for 500 h and that the coke formation on the used catalyst was not observed.

Thermodynamic properties and equilibrium constant of chemical reaction in nanosystem: An theoretical and experimental study

International Nuclear Information System (INIS)

Du, Jianping; Zhao, Ruihua; Xue, Yongqiang

2012-01-01

Highlights: ► There is an obvious influence of the size on thermodynamic properties for the reaction referring nano-reactants. ► Gibbs function, enthalpy, entropy and equilibrium constant are dependent on the reactant size. ► There is an approximate linear relation between them. - Abstract: The theoretical relations of thermodynamic properties, the equilibrium constant and reactant size in nanosystem are described. The effects of size on thermodynamic properties and the equilibrium constant were studied using nanosize zinc oxide and sodium bisulfate solution as a reaction system. The experimental results indicated that the molar Gibbs free energy, the molar enthalpy and the molar entropy of the reaction decrease, but the equilibrium constant increases with decreasing reactant size. Linear trends were observed between the reciprocal of size for nano-reactant and thermodynamic variable, which are consistent with the theoretical relations.

Modelling and experimental evaluation of reaction kinetics in reactive extraction for chiral separation of amines, amino acids and amino-alcohols

NARCIS (Netherlands)

Steensma, M.; Kuipers, N.J.M.; de Haan, A.B.; Kwant, Gerard

2007-01-01

This paper reports on determination of the intrinsic reaction kinetics in reactive extraction of chiral compounds. It is important to know the mass transfer rates and reaction kinetics separately for a reliable scale-up. A kinetic model is developed to interpret the experimental data from the

Use of polymerase chain reaction in the diagnosis of toxocariasis: an experimental study.

Science.gov (United States)

Rai, S K; Uga, S; Wu, Z; Takahashi, Y; Matsumura, T

1997-09-01

In this paper we report the usefulness of polymerase chain reaction technique in the diagnosis of visceral larva migrans in a mouse model. Liver samples obtained from two set of experimentally infected mice (10, 100, 1,000 and 10,000 embryonated Toxocara canis eggs per mouse) along with the eggs of T. canis, T. cati and Ascaris suum were included in this study. Polymerase chain reaction (PCR) was performed using Toxocara primers (SB12). The first PCR product electrophoresis revealed very thin positive bands or no bands in liver samples. However, on second PCR a clear-cut bands were observed. No positive band was shown by A. suum eggs. Our findings thus indicate the usefulness of PCR technic in the diagnosis of visceral larva migrans (VLM) in liver biopsy materials specifically by means of double PCR using the primer SB12.

The hydrogen atom-deuterium molecule reaction: Experimental determination of product quantum state distributions

International Nuclear Information System (INIS)

Rinnen, K.

1989-01-01

The H + H 2 atom exchange reaction (and its isotopic analogs) is the simplest neutral bimolecular chemical reaction because of the small number of electrons in the system and the lightness of the nuclei. The H 3 potential energy surface (PES) is the most accurately known reactive surface (LSTH surface); there have been both quasiclassical trajectory (QCT) and quantal calculations performed on it. This is one of the few systems for which theory is ahead of experiment, and many theoretical predictions await experimental comparison. The H + D 2 → HD + D reaction is studied using thermal D 2 (∼298 K) and translationally hot hydrogen atoms. Photolysis of HI at 266 nm generates H atoms with center-of-mass collision energies of 1.3 and 0.55 eV, both of which are above the classical reaction barrier of 0.42 eV. The rovibrational population distribution of the molecular product is measured by (2+1) resonance-enhanced multiphoton ionization (REMPI). A major effort has been directed toward calibrating the (2+1) REMPI detection procedure, to determine quantitatively the relationship between ion signals and relative quantum state populations for HD. An effusive, high-temperature nozzle has been constructed to populate thermally the high rovibrational levels observed in the reaction. The results are compared to theoretical calculations of the E,F 1 Σ g + - X 1 Σ g + two-photon transition moments. For the H + D 2 reaction, the populations of all energetically accessible HD product levels are measured. Specifically, the following levels are observed: HD(v = 0, J = 0-15), HD(v = 1, J = 0-12), and HD(v = 2, J = 0-8). Of the available energy, 73% is partitioned into product translation, 18% into HD rotation, and 9% into HD vibration

Inverse opal pH sensors with various protic monomers copolymerized with polyhydroxyethylmethacrylate hydrogel

International Nuclear Information System (INIS)

Shin, Jinsub; Han, Sung Gu; Lee, Wonmok

2012-01-01

Highlights: ► We polymerized four different inverse opal pH sensors by using vinyl monomers containing acidic or basic substituents. ► Stepwise swelling response from polyprotic acid sensor was investigated. ► Opposite color changing responses were obtained for acidic and basic sensors. ► Composite pH sensor with wide pH sensing range was fabricated by mixing different monomers. ► Both acid and base sensors show the response time as fast as ∼10 s. - Abstract: pH sensitive inverse opal sensors were synthesized using various vinyl monomers containing acidic or basic substituents. Acrylic acid (AA), vinylphosphonic acid (VPA), vinylimidazole (VI), and dimethylaminoethylmethacrylic acid (DMAEMA) were respectively copolymerized with hydroxyethylmethacrylate (HEMA), the building block monomer of the hydrogel via UV-initiated photopolymerization. Opal templating and subsequent template removal enabled the fabrication of four inverse opal (IO) hydrogel colorimetric sensors, which responded to pH in different fashions. pH-dependent swelling of the IO hydrogel induced the red-shift of the diffracted color. The sensors containing AA or VPA, the proton donating monomers showed the color shifts from green to red with pH increase due to the increased concentration of carboxylate anions bound to the hydrogel. Diprotic VPA sensor exhibited two-step increases of diffracted wavelengths at its pK a1 and pK a2 respectively. The sensors containing proton acceptors, VI and DMAEMA showed the pH-dependent color changes in an opposite way to the AA sensor and the VPA sensor since their ionizations take place by lowering pH due to the protonation at the amino groups. The shapes of pH response curves of VI and DMAEMA sensors were similar but pK b s were different from each other. Optical diffraction responses of four sensors were compared with the calculated concentration ratios of the ionized species to the total monomer with pH variation, and a deswelling effect in the

Experimental determination of the high-temperature rate constant for the reaction of OH with sec-butanol.

Science.gov (United States)

Pang, Genny A; Hanson, Ronald K; Golden, David M; Bowman, Craig T

2012-10-04

The overall rate constant for the reaction of OH with sec-butanol [CH(3)CH(OH)CH(2)CH(3)] was determined from measurements of the near-first-order OH decay in shock-heated mixtures of tert-butylhydroperoxide (as a fast source of OH) with sec-butanol in excess. Three kinetic mechanisms from the literature describing sec-butanol combustion were used to examine the sensitivity of the rate constant determination to secondary kinetics. The overall rate constant determined can be described by the Arrhenius expression 6.97 × 10(-11) exp(-1550/T[K]) cm(3) molecule(-1) s(-1), valid over the temperature range of 888-1178 K. Uncertainty bounds of ±30% were found to adequately account for the uncertainty in secondary kinetics. To our knowledge, the current data represent the first efforts toward an experimentally determined rate constant for the overall reaction of OH with sec-butanol at combustion-relevant temperatures. A rate constant predicted using a structure-activity relationship from the literature was compared to the current data and previous rate constant measurements for the title reaction at atmospheric-relevant temperatures. The structure-activity relationship was found to be unable to correctly predict the measured rate constant at all temperatures where experimental data exist. We found that the three-parameter fit of 4.95 × 10(-20)T(2.66) exp(+1123/T[K]) cm(3) molecule(-1) s(-1) better describes the overall rate constant for the reaction of OH with sec-butanol from 263 to 1178 K.

A combined high-temperature experimental and theoretical kinetic study of the reaction of dimethyl carbonate with OH radicals

KAUST Repository

Khaled, Fathi; Giri, Binod; Szőri, Milá n; Mai, Tam V.-T.; Huynh, Lam K.; Farooq, Aamir

2017-01-01

The reaction kinetics of dimethyl carbonate (DMC) and OH radicals were investigated behind reflected shock waves over the temperature range of 872-1295 K and at pressures near 1.5 atm. Reaction progress was monitored by detecting OH radicals at 306.69 nm using a UV laser absorption technique. The rate coefficients for the reaction of DMC with OH radicals were extracted using a detailed kinetic model developed by Glaude et al. (Proc. Combust. Inst. 2005, 30(1), 1111-1118). The experimental rate coefficients can be expressed in Arrhenius form as: kexpt'l = 5.15 × 10(13) exp(-2710.2/T) cm(3) mol(-1) s(-1). To explore the detailed chemistry of the DMC + OH reaction system, theoretical kinetic analyses were performed using high-level ab initio and master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) calculations. Geometry optimization and frequency calculations were carried out at the second-order Møller-Plesset (MP2) perturbation level of theory using Dunning's augmented correlation consistent-polarized valence double-ζ basis set (aug-cc-pVDZ). The energy was extrapolated to the complete basis set using single point calculations performed at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory. For comparison purposes, additional ab initio calculations were also carried out using composite methods such as CBS-QB3, CBS-APNO, G3 and G4. Our calculations revealed that the H-abstraction reaction of DMC by OH radicals proceeds via an addition elimination mechanism in an overall exothermic process, eventually forming dimethyl carbonate radicals and H2O. Theoretical rate coefficients were found to be in excellent agreement with those determined experimentally. Rate coefficients for the DMC + OH reaction were combined with literature rate coefficients of four straight chain methyl ester + OH reactions to extract site-specific rates of H-abstraction from methyl esters by OH radicals.

Effect of Nano-clay on Rheological and Extrusion Foaming Process of a Block-Copolymerized Polypropylene

Directory of Open Access Journals (Sweden)

Wang Mingyi

2016-01-01

Full Text Available The effects of nano-clay and the corresponding coupling agent maleic anhydride grafted polypropylene (PP-g-MAH on thermal properties, rheological properties and extrusion foaming process of a block-copolymerized polypropylene (B-PP were studied. Supercritical CO2 (SC CO2 was used as the foaming agent with a concentration of 5wt%. Each step of foamed B-PP/ PP-g-MAH/ nano-clay composites processing is addressed, including mixing of the composites, manufacture of the composites, foaming process of the composites and characterization of the cell structure. The results showed that incorporation of nano-clay and PP-g-MAH caused reduced melt strength and complex viscosity of B-PP. However, the heterogeneous nucleation induced by nano-clay and PP-g-MAH improved the maximum foaming expansion ratio and cell-population density of B-PP foam.

Microscale force response and morphology of tunable co-polymerized cytoskeleton networks

Science.gov (United States)

Ricketts, Shea; Yadav, Vikrant; Ross, Jennifer L.; Robertson-Anderson, Rae M.

The cytoskeleton is largely comprised of actin and microtubules that entangle and crosslink to form complex networks and structures, giving rise to nonlinear multifunctional mechanics in cells. The relative concentrations of semiflexible actin filaments and rigid microtubules tune cytoskeleton function, allowing cells to move and divide while maintaining rigidity and resilience. To elucidate this complex tunability, we create in vitro composites of co-polymerized actin and microtubules with actin:microtubule molar ratios of 0:1-1:0. We use optical tweezers and confocal microscopy to characterize the nonlinear microscale force response and morphology of the composites. We optically drag a microsphere 30 μm through varying actin-microtubule networks at 10 μm/s and 20 μm/s, and measure the force the networks exerts to resist the strain and the force relaxation following strain. We use dual-color confocal microscopy to image distinctly-labeled filaments in the networks, and characterize the integration of actin and microtubules, network connectivity, and filament rigidity. We find that increasing the fraction of microtubules in networks non-monotonically increases elasticity and stiffness, and hinders force relaxation by suppressing network mobility and fluctuations. NSF CAREER Award (DMR-1255446), Scialog Collaborative Innovation Award funded by Research Corporation for Scientific Advancement (Grant No. 24192).

Development of experimental method for self-wastage behavior in sodium-water reaction. Development of test rig (SWAT-2R) and study for experimental procedure

International Nuclear Information System (INIS)

Abe, Yuta; Shimoyama, Kazuhito; Kurihara, Akikazu

2014-07-01

In case of water leak from a penetrated crack on a tube of steam generator in the sodium cooled fast reactor (SFR), self-wastage, that increases the size of leak, may take place by corrosion related to chemical reaction between sodium and water. If the self-wastage continues in a certain period of time, the intact tube bundle may be damaged as a result of enlarged leak. For the safety evaluation of the accident, JAEA has been developing the analytical method of self-wastage using the multi-dimensional sodium-water reaction code. Experiments conducted so far used mainly crack-type test pieces. However, reproducibility was limited and it was difficult to evaluate individual effects of the phenomena in detail. This report describes the development of new experimental rig (SWAT-2R). SWAT-2R enables to examine corrosion effecting factors that were ambiguous in the previous studies. The report includes description of development of micro-leak test piece, examination of experimental procedure. The results will provide fundamental data for validation of the self-wastage analytical method. (author)

Synthesis and characterization of starch-g-poly(vinyl acetate-co-butyl acrylate) bio-based adhesive for wood application.

Science.gov (United States)

Zia-Ud-Din; Chen, Lei; Ullah, Ikram; Wang, Peng Kai; Javaid, Allah Bakhsh; Hu, Chun; Zhang, Mengchao; Ahamd, Ishtiaq; Xiong, Hanguo; Wang, Zhenjiong

2018-07-15

Enhancing the performance of wood adhesive is important for its industrial applications. Accordingly, we designed and demonstrated the use of two co-monomers vinyl acetate (VAc) and butyl acrylate (BA) for promoting the graft copolymerization while improving the bonding performance of wood adhesive. The results showed that the addition of co-monomers in the ratio of VAc/BA 6:4 (v/v, volume basis of VAc) could improve the shear strength to 6.68MPa and 3.32MPa in dry and wet states, respectively. 1 H-nuclear magnetic resonance ( 1 H NMR) and fourier transform infrared spectroscopy (FT-IR) analysis revealed successful graft copolymerization reaction while the morphologies were observed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Furthermore, the grafting reaction and thermal stabilities of wood adhesive were analyzed by X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). The results showed that the properties of wood adhesive could improve dramatically by using two co-monomers VAc and BA during the graft copolymerization reaction. Copyright © 2018 Elsevier B.V. All rights reserved.

Analytical applications of the 12C(d,p) reaction. Treatment of experimental spectra

International Nuclear Information System (INIS)

Engerran, J.-A.

1975-01-01

The nuclear (d,p) reaction induced on carbon and oxygen at medium energies (1 to 4MeV) has been used for the determination of very small quantities (less than a monolayer) as well as of the in-depth distribution. With respect to the first feature of this reaction, chemisorption study has been undertaken for the mixture CO/O 2 at the surface of a polycristalline sample of platinum. An adapted irradiation detection set-up is described. Obtaining the in-depth distribution leads to the more general case of treatment of experimental spectra. Owing to the results given by the classical methods of deconvolution or convolution, a joint procedure was chosen for our application. A trial function is determined by a convolutionprocess, to be used as initial function in an iterative method. Convergence is then easily achieved avoiding Gibbs phenomena. As a main application, carbon profile determination is obtained for a boron matrix [fr

LLUSTRATION OF AMINO ACIDS REACTIONS AND PROTEINS CHARACTERIZATION FOR EXPERIMENTAL BIOCHEMISTRY CLASSES

Directory of Open Access Journals (Sweden)

I. Parreira

2008-05-01

Full Text Available New teaching methodologies have been developed to facilitate the learning of biochemistry concepts. A new  approach to Biochemistry  teaching  has become more frequent,  one that does not  require reagents but use photos, videos, softwares etc. Experimental Biochemistry classes, i.e. covering characterization of amino acids and proteins,  might be more productive with the use of complementary didactic material.  Furthermore,  if experiments cannot be implemented, classes may  be well illustrated with complementary didactic material covering from the simplest to the most  complex experiments.  In order to  aid Biochemistry classes without practical experiments, some tests and reactions were documented in our laboratory through digital photos, for  instance: (1 the biuret reaction wherein the blue reagent turns violet in the presence of proteins and changes to pink when combined with short-chain polypeptides; (2 the ninhydrin test used in amino acid analysis of proteins: most of the amino acids are hydrolyzed and react with ninhydrin; when reacting with these free amines, a deep blue or purple color appears; (3 methods for detecting proteins wherein spectrophotometry is used, that deals with the relationship between absorbance, concentration and path length, which constitute the Beer-Lambert Law. A didactic material constituted by texts, schemes and illustrated by photos has been created for each class topic. This material can be used either as a teacher script or in a presentation form to illustrate classes without experimental activities. Financial Support: Pro-Reitoria Graduação-USP, CNPq.

Ethylene homo- and copolymerization chain-transfers: A perspective from supported (n BuCp) 2 ZrCl 2 catalyst active centre distribution

KAUST Repository

Atiqullah, Muhammad

2015-04-01

Polymerization chain termination reactions and unsaturation of the polymer backbone end are related. Therefore, in this study, the parameters resulting from the modelling of the active centre distribution of the supported catalyst - silica/MAO/(nBuCp)2ZrCl2 - were applied to evaluate the active-centre-dependent ethylene homo- and copolymerization rates, as well as the corresponding chain termination rates. This approach, from a microkinetic mechanistic viewpoint, elucidates better the 1-hexene-induced positive comonomer effect and chain transfer phenomenon. The kinetic expressions, developed on the basis of the proposed polymerization mechanisms, illustrate how the active site type-dependent chain transfer phenomenon is influenced by the different apparent termination rate constants and momoner concentrations. The active centre-specific molecular weight M ni (for the above homo- and copolymer), as a function of chain transfer probability, p CTi, varied as follows: log (p C Ti) = log (mwru) - log (Mn i), where mw ru is the molecular weight of the repeat unit. The physical significance of this finding has been explained. The homo- and copolymer backbones showed all the three chain end unsaturations (vinyl, vinylidene, and trans-vinylene). The postulated polymerization mechanisms reveal the underlying polymer chemistry. The results of the present study will contribute to develop in future supported metallocene catalysts that will be useful to synthesize polyethylene precursors having varying chain end unsaturations, which can be eventually used to prepare functional polyethylenes. [Figure not available: see fulltext.] © 2015 Indian Academy of Sciences.

Experimental study o the sodium-concrete reaction

International Nuclear Information System (INIS)

Goncalves, A.C.; Torres, A.R.; Brito Aghina, L.O. de; Messere e Castro, P.

1986-01-01

Effects and aspects of security are verified during a sodium leakage in high temperatures on liners of contention cells and directly on the concrete. As this kinetic process involves reactions between materials in solid state (such as oxides and carbonates) vapors and gases (such as water and CO 2 )) with liquid sodium, effects of each phase of the heterogeneous mixture are separately analysed. Are still analysed produced products and briefly discussed the kinetic of the sodium-concrete reaction. (Author) [pt

Experimental study and nuclear model calculations of {sup 3}He-induced nuclear reactions on zinc

Energy Technology Data Exchange (ETDEWEB)

Al-Abyad, M.; Mohamed, Gehan Y. [Nuclear Research Centre, Atomic Energy Authority, Physics Department (Cyclotron Facility), Cairo (Egypt); Ditroi, F.; Takacs, S.; Tarkanyi, F. [Hungarian Academy of Sciences (ATOMKI), Institute for Nuclear Research, Debrecen (Hungary)

2017-05-15

Excitation functions of {sup 3}He-induced nuclear reactions on natural zinc were measured using the standard stacked-foil technique and high-resolution gamma-ray spectrometry. From their threshold energies up to 27 MeV, the cross-sections for {sup nat}Zn ({sup 3}He,xn) {sup 69}Ge, {sup nat}Zn({sup 3}He,xnp) {sup 66,67,68}Ga, and {sup nat}Zn({sup 3}He,x){sup 62,65}Zn reactions were measured. The nuclear model codes TALYS-1.6, EMPIRE-3.2 and ALICE-IPPE were used to describe the formation of these products. The present data were compared with the theoretical results and with the available experimental data. Integral yields for some important radioisotopes were determined. (orig.)

Curing behavior and reaction kinetics of binder resins for 3D-printing investigated by dielectric analysis (DEA)

Science.gov (United States)

Möginger, B.; Kehret, L.; Hausnerova, B.; Steinhaus, J.

2016-05-01

3D-Printing is an efficient method in the field of additive manufacturing. In order to optimize the properties of manufactured parts it is essential to adapt the curing behavior of the resin systems with respect to the requirements. Thus, effects of resin composition, e.g. due to different additives such as thickener and curing agents, on the curing behavior have to be known. As the resin transfers from a liquid to a solid glass the time dependent ion viscosity was measured using DEA with flat IDEX sensors. This allows for a sensitive measurement of resin changes as the ion viscosity changes two to four decades. The investigated resin systems are based on the monomers styrene and HEMA. To account for the effects of copolymerization in the calculation of the reaction kinetics it was assumed that the reaction can be considered as a homo-polymerization having a reaction order n≠1. Then the measured ion viscosity curves are fitted with the solution of the reactions kinetics - the time dependent degree of conversion (DC-function) - for times exceeding the initiation phase representing the primary curing. The measured ion viscosity curves can nicely be fitted with the DC-function and the determined fit parameters distinguish distinctly between the investigated resin compositions.

Experimental Observation of Nuclear Reactions in Palladium and Uranium

International Nuclear Information System (INIS)

J. Dufour; D. Murat; X. Dufour; J. Foos

2001-01-01

By submitting various metals (Pd, U) containing hydrogen (from 2000 to 700 000 atoms of hydrogen for 1 000 000 atoms of the host metal) to the combined action of electrical currents and magnetic fields, we have observed a sizeable exothermal effect (from 0.1 to 8 W for 500 mg of metal used). This effect is beyond experimental errors, the energy output being typically 130 to 250% of the energy input and not of chemical origin (exothermal effect in the range of 7000 MJ/mol of metal in the case of palladium and of 60 MJ/mol in the case of uranium). New chemical species also appear in the processes metals. It has been shown by a QED calculation that resonances of long lifetime (s), nuclear dimensions (fm), and low energy of formation (eV) could exist. This concept seems to look like the 'shrunken hydrogen atoms' proposed by various authors. It is indeed very different in two ways (a) being a metastable state, it needs energy to be formed (a few eV) and reverts to normal hydrogen after a few seconds, liberating back its energy of formation (it is thus not the source of the energy observed); (b) its formation can be described as the electron spin/proton nuclear spin interaction becoming first order in the lattice environment (whereas it is third order in a normal hydrogen atom). Moreover, we consider that the hydrex cannot yield a neutron because this reaction is strongly endothermic. To explain our results, we put forward the following working hypothesis: In a metal lattice and under proper conditions, the formation of such resonances (metastable state) could be favored. We propose to call them HYDREX, and we assume that they are actually formed in cold fusion (CF) and low-energy nuclear reaction (LENR) experiments. Once formed, a number of HYDREX could gather around a nucleus of the lattice to form a cluster of nuclear size and of very long life time compared to nuclear time (10 -22 s). In this cluster, nuclear rearrangements could take place, yielding mainly 4 He

The reaction between iodine and silver under severe PWR accident conditions. An experimental parameter study

Energy Technology Data Exchange (ETDEWEB)

Funke, F; Greger, G U; Bleier, A; Hellmann, S; Morell, W [Siemens AG, Power Generation Group, Erlangen (Germany)

1996-12-01

An extensive experimental parameter study was performed on the kinetics in the reaction system I{sub 2}/Ag and I{sup -}/Ag in a laboratory-scale apparatus.Starting with I{sub 2} or I{sup -} solutions and silver powder suspensions, the decrease of soluted I{sub 2} or I{sup -}, respectively, due to fixation on the silver particles, was monitored as function of time using the radioactive tracer I-131. The measured data were analyzed using a model of first order kinetics with respect to the iodine concentration. However, the analysis using first order kinetics had to be performed separately in an early, fast reaction phase and in a late, slow reaction phase. The reason for this unexpected behaviour was not identified. Thus, rate constant, two for each test, were deduced from 14 I{sub 2}/Ag main tests and from 36 I{sup -}/Ag tests. No dependencies of the rate constants were found on the parameters temperature, initial iodine concentration, presence of boric acid, type of silver educt, and pretreatment of the silver educt prior to the tests. However, the stirring of the reaction solution generally enhanced the kinetics highlighting the importance of mass transfer. The I{sup -}/Ag reaction proceeded only if there was no inertization of the reaction solution by sparging with nitrogen. The temperature-independent rate constant for the early, fast I{sub 2}/Ag reaction phase is 2E-5 m/s. However, a smaller rate constant of 6E-6 m/s is recommended for use in source term calculations with IMPAIR, which already contains a first order model. Analogously, the temperature-independent I{sup -}/Ag reaction rate constant is 8E-6 m/s in an early, fast reaction phase. For use in source term calculations, a smaller rate constant of 2E-6 m/s is recommended. The lower bound of the I{sup -}/Ag rate constant was 3E-8 m/s which could be used in very conservative source term calculations. (author) 20 figs., 6 tabs., 15 refs.

A combined high-temperature experimental and theoretical kinetic study of the reaction of dimethyl carbonate with OH radicals

KAUST Repository

Khaled, Fathi

2017-02-08

The reaction kinetics of dimethyl carbonate (DMC) and OH radicals were investigated behind reflected shock waves over the temperature range of 872-1295 K and at pressures near 1.5 atm. Reaction progress was monitored by detecting OH radicals at 306.69 nm using a UV laser absorption technique. The rate coefficients for the reaction of DMC with OH radicals were extracted using a detailed kinetic model developed by Glaude et al. (Proc. Combust. Inst. 2005, 30(1), 1111-1118). The experimental rate coefficients can be expressed in Arrhenius form as: kexpt\\'l = 5.15 × 10(13) exp(-2710.2/T) cm(3) mol(-1) s(-1). To explore the detailed chemistry of the DMC + OH reaction system, theoretical kinetic analyses were performed using high-level ab initio and master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) calculations. Geometry optimization and frequency calculations were carried out at the second-order Møller-Plesset (MP2) perturbation level of theory using Dunning\\'s augmented correlation consistent-polarized valence double-ζ basis set (aug-cc-pVDZ). The energy was extrapolated to the complete basis set using single point calculations performed at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory. For comparison purposes, additional ab initio calculations were also carried out using composite methods such as CBS-QB3, CBS-APNO, G3 and G4. Our calculations revealed that the H-abstraction reaction of DMC by OH radicals proceeds via an addition elimination mechanism in an overall exothermic process, eventually forming dimethyl carbonate radicals and H2O. Theoretical rate coefficients were found to be in excellent agreement with those determined experimentally. Rate coefficients for the DMC + OH reaction were combined with literature rate coefficients of four straight chain methyl ester + OH reactions to extract site-specific rates of H-abstraction from methyl esters by OH radicals.

On experimental determination of characteristics of nuclear fusion reactions from mu-molecular resonance states

International Nuclear Information System (INIS)

Bystritskij, V.M.; Pen'kov, F.M.

1997-01-01

Charge-nonsymmetrical deuterium-helium muon complexes (dμHe) are studied. A method is proposed for experimentally determining the rates of nuclear fusion reactions in dμHe molecules in the J=1 and J=0 states (J is the orbital moment of the system) and the partial rates for radiative decay of these complexes in these states. Experiments are supposed to be carried out at meson factories with gaseous and cryogenic targets filled with a mixture of deuterium and helium

Deeply inelastic transfer reactions induced by heavy ions in rare earth targets. II. Interpretation of experimental data

International Nuclear Information System (INIS)

Rivet, M.F.; Bimbot, R.; Ngo, C.

1979-01-01

The experimental angular distributions and cross sections for a series of deeply inelastic transfer reactions induced by various projectiles in rare earth targets have been interpreted using a model which includes a dynamical coupling between relative motion and mass asymmetry and treats statistical fluctuations. As the transfer reactions considered correspond to an increase of the potential energy of the composite system their observation is mainly due to fluctuations. The calculation reproduces correctly the angular distributions, but the cross sections are underestimated. Several effects are discussed which may increase these cross sections and are neglected in the calculation

Experimental study of exclusive $^2$H$(e,e^\\prime p)n$ reaction mechanisms at high $Q^2$

Energy Technology Data Exchange (ETDEWEB)

Kim Egiyan; Gegham Asryan; Nerses Gevorgyan; Keith Griffioen; Jean Laget; Sebastian Kuhn; Gary Adams; Moscov Amaryan; Pawel Ambrozewicz; Marco Anghinolfi; Gerard Audit; Harutyun AVAKIAN; Harutyun Avakian; Hovhannes Baghdasaryan; Nathan Baillie; Jacques Ball; Nathan Baltzell; Steve Barrow; Vitaly Baturin; Marco Battaglieri; Ivan Bedlinski; Ivan Bedlinskiy; Mehmet Bektasoglu; Matthew Bellis; Nawal Benmouna; Barry Berman; Angela Biselli; Lukasz Blaszczyk; Sylvain Bouchigny; Sergey Boyarinov; Robert Bradford; Derek Branford; William Briscoe; William Brooks; Stephen Bueltmann; Volker Burkert; Cornel Butuceanu; John Calarco; Sharon Careccia; Daniel Carman; Antoine Cazes; Shifeng Chen; Philip Cole; Patrick Collins; Philip Coltharp; Dieter Cords; Pietro Corvisiero; Donald Crabb; Volker Crede; John Cummings; Natalya Dashyan; Rita De Masi; Raffaella De Vita; Enzo De Sanctis; Pavel Degtiarenko; Haluk Denizli; Lawrence Dennis; Alexandre Deur; Kahanawita Dharmawardane; Richard Dickson; Chaden Djalali; Gail Dodge; Joseph Donnelly; David Doughty; Michael Dugger; Steven Dytman; Oleksandr Dzyubak; Hovanes Egiyan; Lamiaa Elfassi; Latifa Elouadrhiri; Paul Eugenio; Renee Fatemi; Gleb Fedotov; Gerald Feldman; Robert Feuerbach; Robert Fersch; Michel Garcon; Gagik Gavalian; Gerard Gilfoyle; Kevin Giovanetti; Francois-Xavier Girod; John Goetz; Atilla Gonenc; Christopher Gordon; Ralf Gothe; Michel Guidal; Matthieu Guillo; Hayko Guler; Lei Guo; Vardan Gyurjyan; Cynthia Hadjidakis; Kawtar Hafidi; Hayk Hakobyan; Rafael Hakobyan; Charles Hanretty; John Hardie; F. Hersman; Kenneth Hicks; Ishaq Hleiqawi; Maurik Holtrop; Charles Hyde-Wright; Yordanka Ilieva; David Ireland; Boris Ishkhanov; Eugeny Isupov; Mark Ito; David Jenkins; Hyon-Suk Jo; Kyungseon Joo; Henry Juengst; Narbe Kalantarians; James Kellie; Mahbubul Khandaker; Wooyoung Kim; Andreas Klein; Franz Klein; Alexei Klimenko; Mikhail Kossov; Zebulun Krahn; Laird Kramer; V. Kubarovsky; Joachim Kuhn; Sergey Kuleshov; Jeff Lachniet; Jorn Langheinrich; David Lawrence; Ji Li; Kenneth Livingston; Haiyun Lu; Marion MacCormick; Claude Marchand; Nikolai Markov; Paul Mattione; Simeon McAleer; Bryan McKinnon; John McNabb; Bernhard Mecking; Surik Mehrabyan; Joseph Melone; Mac Mestayer; Curtis Meyer; Tsutomu Mibe; Konstantin Mikhaylov; Ralph Minehart; Marco Mirazita; Rory Miskimen; Viktor Mokeev; Kei Moriya; Steven Morrow; Maryam Moteabbed; James Mueller; Edwin Munevar Espitia; Gordon Mutchler; Pawel Nadel-Turonski; Rakhsha Nasseripour; Silvia Niccolai; Gabriel Niculescu; Maria-Ioana Niculescu; Bogdan Niczyporuk; Megh Niroula; Rustam Niyazov; Mina Nozar; Grant O' Rielly; Mikhail Osipenko; Alexander Ostrovidov; Kijun Park; Evgueni Pasyuk; Craig Paterson; Sergio Pereira; Joshua Pierce; Nikolay Pivnyuk; Dinko Pocanic; Oleg Pogorelko; Sergey Pozdnyakov; Barry Preedom; John Price; Yelena Prok; Dan Protopopescu; Brian Raue; Gregory Riccardi; Giovanni Ricco; Marco Ripani; Barry Ritchie; Federico Ronchetti; Guenther Rosner; Patrizia Rossi; Franck Sabatie; Julian Salamanca; Carlos Salgado; Joseph Santoro; Vladimir Sapunenko; Reinhard Schumacher; Vladimir Serov; Youri Sharabian; Nikolay Shvedunov; Alexander Skabelin; Elton Smith; Lee Smith; Daniel Sober; Daria Sokhan; Aleksey Stavinskiy; Samuel Stepanyan; Stepan Stepanyan; Burnham Stokes; Paul Stoler; Steffen Strauch; Mauro Taiuti; David Tedeschi; Ulrike Thoma; Avtandil Tkabladze; Svyatoslav Tkachenko; Luminita Todor; Clarisse Tur; Maurizio Ungaro; Michael Vineyard; Alexander Vlassov; Daniel Watts; Lawrence Weinstein; Dennis Weygand; M. Williams; Elliott Wolin; Michael Wood; Amrit Yegneswaran; Lorenzo Zana; Jixie Zhang; Bo Zhao; Zhiwen Zhao

2007-06-01

The reaction {sup 2}H(e,e{prime} p)n has been studied with full kinematic coverage for photon virtuality 1.75 < 5.5 {approx} GeV{sup 2}. Comparisons of experimental data with theory indicate that for very low values of neutron recoil momentum (p{sub n} < 100 MeV/c) the neutron is primarily a spectator and the reaction can be described by the plane-wave impulse approximation. For 100 < 750 MeV/c proton-neutron rescattering dominates the cross section, while {Delta} production followed by the N{Delta} {yields} NN transition is the primary contribution at higher momenta.

Nuclear reactions as structure probes

International Nuclear Information System (INIS)

Fernandez, Bernard; Cugnon, Joseph; Roussel-Chomaz, Patricia; Sparenberg, Jean-Marc; Oliveira Santos, Francois de; Bauge, Eric; Poves, Alfredo; Keeley, Nicholas; Simenel, Cedric; Avez, Benoit; Lacroix, Denis; Baye, Daniel; Cortina-Gil, Dolores; Pons, Alexandre

2007-09-01

This publication gathers courses which aim at giving a view on new experiments which are performed by using radioactive beams, notably low intensity beams, in different accelerators, and allow the structure of very exotic nuclei to be characterized. Experimental as well as theoretical aspects are thus addressed. The contributions propose: a brief history of nuclear reactions and of instruments used to study them from the discovery of nucleus to the DWBA (Distorted Wave Born Approximation); an overview of nuclear reactions; experimental techniques; the theory of collisions at low energy; resonant elastic scattering, inelastic scattering and astrophysical reactions; to probe nuclear structure with nucleons; shell model and spectroscopic factors; analysis of transfer reactions and determination of spectroscopic factors; microscopic approaches of nuclear dynamics; theoretical aspects of dissociation reactions; experimental aspects of knockout reactions; research in oenology with the chemical characterisation of defective ageing of dry white wines

Experimental setup and procedure for the measurement of the 7Be(n,p)7Li reaction at n_TOF

Science.gov (United States)

Barbagallo, M.; Andrzejewski, J.; Mastromarco, M.; Perkowski, J.; Damone, L. A.; Gawlik, A.; Cosentino, L.; Finocchiaro, P.; Maugeri, E. A.; Mazzone, A.; Dressler, R.; Heinitz, S.; Kivel, N.; Schumann, D.; Colonna, N.; Aberle, O.; Amaducci, S.; Audouin, L.; Bacak, M.; Balibrea, J.; Bečvář, F.; Bellia, G.; Berthoumieux, E.; Billowes, J.; Bosnar, D.; Brown, A.; Caamaño, M.; Calviño, F.; Calviani, M.; Cano-Ott, D.; Cardella, R.; Casanovas, A.; Cerutti, F.; Chen, Y. H.; Chiaveri, E.; Cortés, G.; Cortés-Giraldo, M. A.; Cristallo, S.; Diakaki, M.; Dietz, M.; Domingo-Pardo, C.; Dupont, E.; Durán, I.; Fernández-Domínguez, B.; Ferrari, A.; Ferreira, P.; Furman, V.; Göbel, K.; García, A. R.; Gilardoni, S.; Glodariu, T.; Gonçalves, I. F.; González-Romero, E.; Griesmayer, E.; Guerrero, C.; Gunsing, F.; Harada, H.; Heyse, J.; Jenkins, D. G.; Jericha, E.; Johnston, K.; Käppeler, F.; Kadi, Y.; Kalamara, A.; Kavrigin, P.; Kimura, A.; Kokkoris, M.; Krtička, M.; Kurtulgil, D.; Leal-Cidoncha, E.; Lederer, C.; Leeb, H.; Lerendegui-Marco, J.; Lo Meo, S.; Lonsdale, S. J.; Macina, D.; Manna, A.; Marganiec, J.; Martínez, T.; Martins-Correia, J. G.; Masi, A.; Massimi, C.; Mastinu, P.; Mendoza, E.; Mengoni, A.; Milazzo, P. M.; Mingrone, F.; Musumarra, A.; Negret, A.; Nolte, R.; Oprea, A.; Pappalardo, A. D.; Patronis, N.; Pavlik, A.; Piscopo, M.; Porras, I.; Praena, J.; Quesada, J. M.; Radeck, D.; Rauscher, T.; Reifarth, R.; Robles, M. S.; Rubbia, C.; Ryan, J. A.; Sabaté-Gilarte, M.; Saxena, A.; Schell, J.; Schillebeeckx, P.; Sedyshev, P.; Smith, A. G.; Sosnin, N. V.; Stamatopoulos, A.; Tagliente, G.; Tain, J. L.; Tarifeño-Saldivia, A.; Tassan-Got, L.; Valenta, S.; Vannini, G.; Variale, V.; Vaz, P.; Ventura, A.; Vlachoudis, V.; Vlastou, R.; Wallner, A.; Warren, S.; Weiss, C.; Woods, P. J.; Wright, T.; Žugec, P.

2018-04-01

Following the completion of the second neutron beam line and the related experimental area (EAR2) at the n_TOF spallation neutron source at CERN, several experiments were planned and performed. The high instantaneous neutron flux available in EAR2 allows to investigate neutron induced reactions with charged particles in the exit channel even employing targets made out of small amounts of short-lived radioactive isotopes. After the successful measurement of the 7Be(n, α) α cross section, the 7Be(n,p)7Li reaction was studied in order to provide still missing cross section data of relevance for Big Bang Nucleosynthesis (BBN), in an attempt to find a solution to the cosmological Lithium abundance problem. This paper describes the experimental setup employed in such a measurement and its characterization.

Use of additives to fine-tune the composition of carbonate units in the polymer formed by copolymerization of co2 with epoxide: application to the synthesis of polycarbonate-based block copolymers and of telechelics

KAUST Repository

Feng, Xiaoshuang

2016-12-22

Embodiments of the present disclosure describe a method of making a polycarbonate, comprising contacting one or more cyclic monomers and carbon dioxide in the presence of one or more of a Lewis acid catalyst, an initiator, and an ionic liquid; and agitating, sufficient to copolymerize the one or more cyclic monomers and carbon dioxide to create a polycarbonate. Embodiments of the present disclosure further describe a method of controlling a polymer composition, comprising contacting one or more cyclic monomers and carbon dioxide; adjusting an amount of one or more of a Lewis acid catalyst, an ionic liquid, and an initiator in the presence of the one or more cyclic monomers and carbon dioxide, sufficient to selectively modify a resulting polycarbonate; and agitating, sufficient to copolymerize the one or more cyclic monomers and carbon dioxide to create the polycarbonate.

Use of additives to fine-tune the composition of carbonate units in the polymer formed by copolymerization of co2 with epoxide: application to the synthesis of polycarbonate-based block copolymers and of telechelics

KAUST Repository

Feng, Xiaoshuang; Zhang, Dongyue; Gnanou, Yves; Hadjichristidis, Nikolaos

2016-01-01

Embodiments of the present disclosure describe a method of making a polycarbonate, comprising contacting one or more cyclic monomers and carbon dioxide in the presence of one or more of a Lewis acid catalyst, an initiator, and an ionic liquid; and agitating, sufficient to copolymerize the one or more cyclic monomers and carbon dioxide to create a polycarbonate. Embodiments of the present disclosure further describe a method of controlling a polymer composition, comprising contacting one or more cyclic monomers and carbon dioxide; adjusting an amount of one or more of a Lewis acid catalyst, an ionic liquid, and an initiator in the presence of the one or more cyclic monomers and carbon dioxide, sufficient to selectively modify a resulting polycarbonate; and agitating, sufficient to copolymerize the one or more cyclic monomers and carbon dioxide to create the polycarbonate.

Experimental data on fission and (n,xn) reactions; Donnees experimentales de fission et de reactions (n,xn)

Energy Technology Data Exchange (ETDEWEB)

Belier, G.; Chatillon, A.; Granier, T.; Laborie, J.M.; Laurent, B.; Ledoux, X.; Taieb, J.; Varignon, C.; Bauge, E.; Bersillon, O.; Aupiais, J.; Le Petit, G. [CEA Bruyeres-le-Chatel, 91 (France); Authier, N.; Casoli, P. [CEA Valduc, 21 - Is-sur-Tille (France)

2011-07-15

Investigations on neutron-induced fission of actinides and the deuteron breakup are presented. Neutron-induced fission has been studied for 10 years at the WNR (Weapons Neutron Research) neutron facility of the Los Alamos Neutron Science Center (LANSCE). Thanks to this white neutron source the evolution of the prompt fission neutron energy spectra as a function of the incident neutron energy has been characterized in a single experiment up to 200 MeV incident energy. For some isotopes the prompt neutron multiplicity has been extracted. These experimental results demonstrated the effect on the mean neutron energy of the neutron emission before scission for energies higher than the neutron binding energy. This extensive program ({sup 235}U and {sup 238}U, {sup 239}Pu, {sup 237}Np and {sup 232}Th were measured) is completed by neutron spectra measurements on the CEA 4 MV accelerator. The D(n,2n) reaction is studied both theoretically and experimentally. The cross-section was calculated for several nucleon-nucleon interactions including the AV18 interaction. It has also been measured on the CEA 7 MV tandem accelerator at incident neutron energies up to 25 MeV. Uncertainties lower than 8% between 5 and 10 MeV were obtained. In particular these experiments have extended the measured domain for cross sections. (authors)

Experimental Investigation of Gaseous Reaction Products from Na-CO{sub 2} Reaction in Na/CO{sub 2} Heat Exchanger leakage scenario

Energy Technology Data Exchange (ETDEWEB)

Go, A-Reum; Jung, Hwa-Young; Kim, Min Seok; Lee, Jeong Ik [KAIST, Daejeon (Korea, Republic of); Min, Jaehong; Wi, Myung-Hwan [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

2015-10-15

The SFRs have operated with the steam Rankine cycle as a power conversion system. However, the potential sodium-water reaction (SWR) whose chemical reactivity is vigorous and instantaneous has been one of the major issues concerning the safety and integrity of the SFRs. In order to avoid SWR, supercritical CO{sub 2}(S-CO{sub 2}) Brayton cycles have been investigated recently. Compared to conventional steam Rankine cycles, S-CO{sub 2} Brayton cycle features higher thermal efficiency and potential compactness of its required equipment. In spite of the superiority of S-CO{sub 2} Brayton cycle, there is a potential reactive process between sodium and CO{sub 2} if the pressure boundary fails in the sodium-CO{sub 2} heat exchanger. The leakage scenario which could lead to mechanical and thermal problems should be evaluated. Previous studies have reported the following major reaction formulas. Each reaction occurs competitively. In this paper, the experimental setup to observe the pressure variation and CO concentration in Na-CO{sub 2} heat exchanger during the CO{sub 2} leak is explained. Before the experiment is carried out, water-CO{sub 2} mock-up test will be performed. In order to evaluate the leakage scenario in Na-CO{sub 2} heat exchanger more accurately, this study will be important for guaranteeing the system of SFR coupled with S-CO{sub 2} cycle.

Drug delivery system prepared by ionizing radiation of the N,N-dimethyl acrylamide with acryloyloxy-acetanilide copolymerization

International Nuclear Information System (INIS)

Martellini, Flavia; Higa, Olga Z.; Queiroz, Alvaro A.A. de; Rodighiero, Paolo

1995-01-01

Radiation induced polymerization has been used in biomaterials used in systems which such as drug delivery (DDS). This work describes the copolymerization of the monomers by gamma rays N,N-dimethyl acrylamide (DMAA) and acryloyloxy-acetanilide (AOA) for the immobilization of paracetamol, an analgesic and anti thermic drug. Dimethylformamide solutions were used in two concentrations of DMAA and AOA (F DMAA/AOA = 0,85/015 and 0,70/0,30, where F = molar fraction in the monomer feed). The samples were irradiated in the dose range of 30-800 Gy. The copolymer poly(DMAA-co-AOA) characterization was carried out by FTIR and 1 HRMN. The hydrolysis was studied considering the formation of sodium salts of 4-hydroxy acetanilide at different times of treatment using colorimetric assay. (author). 6 refs., 5 figs

Highly selective micro-sequential injection lab-on-valve (μSI-LOV) method for determination of ultra trace concentrations of nickel in saline matrices using detection by electrothermal atomic absorption spectrometr

DEFF Research Database (Denmark)

Long, Xiangbao; Miró, Manuel; Jensen, Rikard

2006-01-01

of the LOV to assure sufficient reaction time for the formation of Ni(DMG)2 chelate. The non-ionic coordination compound is then collected in a renewable micro-column packed with a reversed-phase copolymeric sorbent [namely, poly(divinylbenzene-co-N-vinylpyrrolidone)] containing a balanced ratio...... water of high hardness and local seawater. Satisfying recoveries were achieved for all spiked environmental water samples with maximum deviations of 6%. The experimental results for the standard reference material were not statistically different to the certified value at a significance level of 0.05....

Nucleon transfer reactions with radioactive beams

Science.gov (United States)

Wimmer, K.

2018-03-01

Transfer reactions are a valuable tool to study the single-particle structure of nuclei. At radioactive beam facilities transfer reactions have to be performed in inverse kinematics. This creates a number of experimental challenges, but it also has some advantages over normal kinematics measurements. An overview of the experimental and theoretical methods for transfer reactions, especially with radioactive beams, is presented. Recent experimental results and highlights on shell evolution in exotic nuclei are discussed.

Statistical analysis of nitrogen-containing vinyl copolymers: radiation-induced copolymerization of vinyl acetate and N-vinyl-2-pyrrolidone

International Nuclear Information System (INIS)

Peppas, N.A.; Gehr, T.W.B.

1979-01-01

Radiation-induced copolymerization of vinyl acetate and N-vinyl-2-pyrrolidone was carried out at 5 0 C using γ-irradiation of 1450 rads/min. Copolymers prepared at conversions lower than 5% were analyzed by a saponification technique. Various linear and nonlinear statistical analysis techniques were used to determine the reactivity ratios of this system as r 1 = 0.348 and r 2 = 3.108. These data were examined and analyzed in relation to problems of elemental analysis involving nitrogen-containing copolymers and to discrepancies in the reactivity ratios obtained by previous investigators. The presence of oxygen and a higher dose rate did not affect the copolymer composition within statistical error. Hydrolyzed copolymers prepared by this method have potential applications as biocompatible materials

An Experimental and Theoretical Study on the Kinetic Isotope Effect of C2H6 and C2D6 Reaction with OH

KAUST Repository

Khaled, Fathi; Giri, Binod; Szőri, Milá n; Viskolcz, Bé la; Farooq, Aamir

2015-01-01

We report experimental and theoretical results for the deuterated kinetic isotope effect (DKIE) of the reaction of OH with ethane (C2H6) and deuterated ethane (C2D6). The reactions were investigated behind reflected shock waves over 800–1350 K by monitoring OH radicals near 306.69 nm using laser absorption. In addition, high level CCSD(T)/cc-pV(T,Q)Z//MP2/cc-pVTZ quantum chemical and statistical rate theory calculations were performed which agreed very well with the experimental findings. The results reported herein provide the first experimental evidence that DKIE for alkanes asymptotes to a value of 1.4 at high temperatures.

An Experimental and Theoretical Study on the Kinetic Isotope Effect of C2H6 and C2D6 Reaction with OH

KAUST Repository

Khaled, Fathi

2015-10-30

We report experimental and theoretical results for the deuterated kinetic isotope effect (DKIE) of the reaction of OH with ethane (C2H6) and deuterated ethane (C2D6). The reactions were investigated behind reflected shock waves over 800–1350 K by monitoring OH radicals near 306.69 nm using laser absorption. In addition, high level CCSD(T)/cc-pV(T,Q)Z//MP2/cc-pVTZ quantum chemical and statistical rate theory calculations were performed which agreed very well with the experimental findings. The results reported herein provide the first experimental evidence that DKIE for alkanes asymptotes to a value of 1.4 at high temperatures.

A comprehensive collection of experimentally validated primers for Polymerase Chain Reaction quantitation of murine transcript abundance

Directory of Open Access Journals (Sweden)

Wang Xiaowei

2008-12-01

Full Text Available Abstract Background Quantitative polymerase chain reaction (QPCR is a widely applied analytical method for the accurate determination of transcript abundance. Primers for QPCR have been designed on a genomic scale but non-specific amplification of non-target genes has frequently been a problem. Although several online databases have been created for the storage and retrieval of experimentally validated primers, only a few thousand primer pairs are currently present in existing databases and the primers are not designed for use under a common PCR thermal profile. Results We previously reported the implementation of an algorithm to predict PCR primers for most known human and mouse genes. We now report the use of that resource to identify 17483 pairs of primers that have been experimentally verified to amplify unique sequences corresponding to distinct murine transcripts. The primer pairs have been validated by gel electrophoresis, DNA sequence analysis and thermal denaturation profile. In addition to the validation studies, we have determined the uniformity of amplification using the primers and the technical reproducibility of the QPCR reaction using the popular and inexpensive SYBR Green I detection method. Conclusion We have identified an experimentally validated collection of murine primer pairs for PCR and QPCR which can be used under a common PCR thermal profile, allowing the evaluation of transcript abundance of a large number of genes in parallel. This feature is increasingly attractive for confirming and/or making more precise data trends observed from experiments performed with DNA microarrays.

Explore the reaction mechanism of the Maillard reaction: a density functional theory study.

Science.gov (United States)

Ren, Ge-Rui; Zhao, Li-Jiang; Sun, Qiang; Xie, Hu-Jun; Lei, Qun-Fang; Fang, Wen-Jun

2015-05-01

The mechanism of Maillard reaction has been investigated by means of density functional theory calculations in the gaseous phase and aqueous solution. The Maillard reaction is a cascade of consecutive and parallel reaction. In the present model system study, glucose and glycine were taken as the initial reactants. On the basis of previous experimental results, the mechanisms of Maillard reaction have been proposed, and the possibility for the formation of different compounds have been evaluated through calculating the relative energy changes for different steps of reaction under different pH conditions. Our calculations reveal that the TS3 in Amadori rearrangement reaction is the rate-determining step of Maillard reaction with the activation barriers of about 66.7 and 68.8 kcal mol(-1) in the gaseous phase and aqueous solution, respectively. The calculation results are in good agreement with previous studies and could provide insights into the reaction mechanism of Maillard reaction, since experimental evaluation of the role of intermediates in the Maillard reaction is quite complicated.

Synthesis of Citric-Acrylate Oligomer and its in-Situ Reaction with Chrome Tanned Collagen (hide powder)

International Nuclear Information System (INIS)

Haroun, A.A.; Masoud, R.A.; Bronco, S.; Ciardelli, F.

2005-01-01

The purpose of this study was to formulate the new combined system of acrylic and citric acids, which has been prepared by free radical polymerization and esterification reaction at the same time to form citric acrylate (CAC) oligomer through ester linkage and low molecular weight (Mw 2241), in compared with polyacrylic acid. The chemical structure and the reaction mechanism of this oligomer were confirmed by different spectroscopic tools (1 H , 13 C-NMR, ATR-IR), gel permeation chromatography and thermogravimetric analysis (TGA/DTA). The problem of the effect of the masking agents in the chrome tanning of the collagen and the pickling of the hide has been approached from the study of the hydrothermal and mechanical properties, using this new eco-friendly oligomer, which was carried out in-situ treated/grafted chrome tanned collagen (hide powder), and pickled hide. The microemulsion grafting copolymerization of (CAC) using 2.2-azo-bis isobutyronitrile (ABIN), via direct coupling reaction, onto the chrome tanned collagen showed that the free amino groups of the collagen were considered to be a potential site for the in-situ reaction with (CAC) oligomer. Also, using of citric-acrylate (CAC) oligomer, during chrome tanning of leather, instead of the traditional strong acids (sulfuric, hydrochloric and formic) resulted in significant improvement in chrome exhaustion and physical properties

In vivo non-invasive optical imaging of temperature-sensitive co-polymeric nanohydrogel

Science.gov (United States)

Chen, Haiyan; Zhang, Jian; Qian, Zhiyu; Liu, Fei; Chen, Xinyang; Hu, Yuzhu; Gu, Yueqing

2008-05-01

Assessment of hyperthermia in pathological tissue is a promising strategy for earlier diagnosis of malignant tumors. In this study, temperature-sensitive co-polymeric nanohydrogel poly(N-isopropylacrylamide-co-acrylic acid) (PNIPA-co-AA) was successfully synthesized by the precipitation polymerization method. The diameters of nanohydrogels were controlled to be less than 100 nm. Also the lower critical solution temperature (LCST, 40 °C) was manipulated above physiological temperature after integration of near-infrared (NIR) organic dye (heptamethine cyanine dye, HMCD) within its interior cores. NIR laser light (765 nm), together with sensitive charge coupled device (CCD) cameras, were designed to construct an NIR imaging system. The dynamic behaviors of PNIPA-co-AA-HMCD composites in denuded mice with or without local hyperthermia treatment were real-time monitored by an NIR imager. The results showed that the PNIPA-co-AA-HMCD composites accumulated in the leg treated with local heating and diffused much slower than that in the other leg without heating. The results demonstrated that the temperature-responsive PNIPA-co-AA-HMCD composites combining with an NIR imaging system could be an effective temperature mapping technique, which provides a promising prospect for earlier tumor diagnosis and thermally related therapeutic assessment.

In vivo non-invasive optical imaging of temperature-sensitive co-polymeric nanohydrogel

International Nuclear Information System (INIS)

Chen Haiyan; Hu Yuzhu; Zhang Jian; Liu Fei; Chen Xinyang; Gu Yueqing; Qian Zhiyu

2008-01-01

Assessment of hyperthermia in pathological tissue is a promising strategy for earlier diagnosis of malignant tumors. In this study, temperature-sensitive co-polymeric nanohydrogel poly(N-isopropylacrylamide-co-acrylic acid) (PNIPA-co-AA) was successfully synthesized by the precipitation polymerization method. The diameters of nanohydrogels were controlled to be less than 100 nm. Also the lower critical solution temperature (LCST, 40 deg. C) was manipulated above physiological temperature after integration of near-infrared (NIR) organic dye (heptamethine cyanine dye, HMCD) within its interior cores. NIR laser light (765 nm), together with sensitive charge coupled device (CCD) cameras, were designed to construct an NIR imaging system. The dynamic behaviors of PNIPA-co-AA-HMCD composites in denuded mice with or without local hyperthermia treatment were real-time monitored by an NIR imager. The results showed that the PNIPA-co-AA-HMCD composites accumulated in the leg treated with local heating and diffused much slower than that in the other leg without heating. The results demonstrated that the temperature-responsive PNIPA-co-AA-HMCD composites combining with an NIR imaging system could be an effective temperature mapping technique, which provides a promising prospect for earlier tumor diagnosis and thermally related therapeutic assessment

Kinetic studies of elementary chemical reactions

Energy Technology Data Exchange (ETDEWEB)

Durant, J.L. Jr. [Sandia National Laboratories, Livermore, CA (United States)

1993-12-01

This program concerning kinetic studies of elementary chemical reactions is presently focussed on understanding reactions of NH{sub x} species. To reach this goal, the author is pursuing experimental studies of reaction rate coefficients and product branching fractions as well as using electronic structure calculations to calculate transition state properties and reaction rate calculations to relate these properties to predicted kinetic behavior. The synergy existing between the experimental and theoretical studies allow one to gain a deeper insight into more complex elementary reactions.

RAFT Dispersion Alternating Copolymerization of Styrene with N-Phenylmaleimide: Morphology Control and Application as an Aqueous Foam Stabilizer

Science.gov (United States)

2016-01-01

We report a new nonaqueous polymerization-induced self-assembly (PISA) formulation based on the reversible addition–fragmentation chain transfer (RAFT) dispersion alternating copolymerization of styrene with N-phenylmaleimide using a nonionic poly(N,N-dimethylacrylamide) stabilizer in a 50/50 w/w ethanol/methyl ethyl ketone (MEK) mixture. The MEK cosolvent is significantly less toxic than the 1,4-dioxane cosolvent reported previously [YangP.; Macromolecules2013, 46, 8545−8556]. The core-forming alternating copolymer block has a relatively high glass transition temperature (Tg), which leads to vesicular morphologies being observed during PISA, as well as the more typical sphere and worm phases. Each of these copolymer morphologies has been characterized by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) studies. TEM studies reveal micrometer-sized elliptical particles with internal structure, with SAXS analysis suggesting an oligolamellar vesicle morphology. This structure differs from that previously reported for a closely related PISA formulation utilizing a poly(methacrylic acid) stabilizer block for which unilamellar platelet-like particles are observed by TEM and SAXS. This suggests that interlamellar interactions are governed by the nature of the steric stabilizer layer. Moreover, using the MEK cosolvent also enables access to a unilamellar vesicular morphology, despite the high Tg of the alternating copolymer core-forming block. This was achieved by simply conducting the PISA synthesis at a higher temperature for a longer reaction time (80 °C for 24 h). Presumably, MEK solvates the core-forming block more than the previously utilized 1,4-dioxane cosolvent, which leads to greater chain mobility. Finally, preliminary experiments indicate that the worms are much more efficient stabilizers for aqueous foams than either the spheres or the oligolamellar elliptical vesicles. PMID:27708458

Poly(propylene carbonate): Insight into the Microstructure and Enantioselective Ring-Opening Mechanism

KAUST Repository

Salmeia, Khalifah A.

2012-11-13

Different poly(propylene carbonate) (PPC) microstructures have been synthesized from the alternating copolymerization of CO 2 with both racemic propylene oxide (PO) and various mixtures of PO enantiomers using chiral salen catalysts. The microstructures of the obtained copolymers as a function of polymerization time have been analyzed by a combination of chiral GC and high-resolution NMR spectroscopy. The 13C NMR spectra of selected poly(propylene carbonate) samples were recorded using a 900 MHz ( 1H) spectrometer, showing a previously unreported fine splitting of the carbonate resonances. This allowed a detailed assignment of signals for various copolymer microstructures taking into account the specifics in their stereo- and regioirregularities. For example, the enantioselectivity preference of the (R,R-salen)Co catalyst for (S)-PO at the beginning of the copolymerization leads predominantly to (S)-PO insertion, with any (R)-PO misinsertion being followed by incorporation of (S)-PO, so that the microstructure features isolated stereoerrors. K rel calculations for the copolymerization showed around 5-fold enantioselectivity for (S)-PO over (R)-PO at short reaction time. Analysis of the copolymer microstructures obtained under various reaction conditions appears to be an additional approach to differentiate the occurrence of bimetallic and bifunctional copolymerization mechanisms that are widely discussed in the literature. © 2012 American Chemical Society.

Poly(propylene carbonate): Insight into the Microstructure and Enantioselective Ring-Opening Mechanism

KAUST Repository

Salmeia, Khalifah A.; Vagin, Sergei; Anderson, Carly E.; Rieger, Bernhard

2012-01-01

Different poly(propylene carbonate) (PPC) microstructures have been synthesized from the alternating copolymerization of CO 2 with both racemic propylene oxide (PO) and various mixtures of PO enantiomers using chiral salen catalysts. The microstructures of the obtained copolymers as a function of polymerization time have been analyzed by a combination of chiral GC and high-resolution NMR spectroscopy. The 13C NMR spectra of selected poly(propylene carbonate) samples were recorded using a 900 MHz ( 1H) spectrometer, showing a previously unreported fine splitting of the carbonate resonances. This allowed a detailed assignment of signals for various copolymer microstructures taking into account the specifics in their stereo- and regioirregularities. For example, the enantioselectivity preference of the (R,R-salen)Co catalyst for (S)-PO at the beginning of the copolymerization leads predominantly to (S)-PO insertion, with any (R)-PO misinsertion being followed by incorporation of (S)-PO, so that the microstructure features isolated stereoerrors. K rel calculations for the copolymerization showed around 5-fold enantioselectivity for (S)-PO over (R)-PO at short reaction time. Analysis of the copolymer microstructures obtained under various reaction conditions appears to be an additional approach to differentiate the occurrence of bimetallic and bifunctional copolymerization mechanisms that are widely discussed in the literature. © 2012 American Chemical Society.

Experimental Cross Sections for Reactions of Heavy Ions and ²⁰⁸Pb, ²⁰⁹Bi, ²³⁸U, and ²⁴⁸Cm Targets

Energy Technology Data Exchange (ETDEWEB)

Patin, Joshua Barnes [Univ. of California, Berkeley, CA (United States)

2002-01-01

The study of the reactions between heavy ions and ²⁰⁸Pb, ²⁰⁹Bi, ²³⁸U, and ²⁴⁸Cm Cm targets was performed to look at the differences between the cross sections of hot and cold fusion reactions. Experimental cross sections were compared with predictions from statistical computer codes to evaluate the effectiveness of the computer code in predicting production cross sections. Hot fusion reactions were studied with the MG system, catcher foil techniques and the Berkeley Gas-filled Separator (BGS). 3n- and 4n-exit channel production cross sections were obtained for the ²³⁸U(¹⁸O,xn)^256-xFm, ²³⁸U(²²Ne,xn)^260-xNo, and ²⁴⁸Cm(¹⁵N,xn)^263-xLr reactions and are similar to previous experimental results. The experimental cross sections were accurately modeled by the predictions of the HIVAP code using the Reisdorf and Schaedel parameters and are consistent with the existing systematics of 4n exit channel reaction products. Cold fusion reactions were examined using the BGS. The ⁴⁸Pb(²³⁸Ca,xn)^256-xNo, ²⁰⁸Pb(⁵⁰Ti,xn)^258-xRf, ²⁰⁸Pb(⁵¹V,xn)^259-xDb, ⁵⁰Bi(²³⁸Ti,xn)^259-xDb, and ²⁰⁹Bi(⁵¹V,xn)^260-xSg reactions were studied. The experimental production cross sections are in agreement with the results observed in previous experiments. It was necessary to slightly alter the Reisdorf and Schaedel parameters for use in the HIVAP code in order to more accurately model the experimental data. The cold fusion experimental results are in agreement with current 1n- and 2n-exit channel systematics.

Preequilibrium Nuclear Reactions

International Nuclear Information System (INIS)

Strohmaier, B.

1988-01-01

After a survey on existing experimental data on precompound reactions and a description of preequilibrium reactions, theoretical models and quantum mechanical theories of preequilibrium emission are presented. The 25 papers of this meeting are analyzed separately

Integrating reaction and analysis: investigation of higher-order reactions by cryogenic trapping

Directory of Open Access Journals (Sweden)

Skrollan Stockinger

2013-09-01

Full Text Available A new approach for the investigation of a higher-order reaction by on-column reaction gas chromatography is presented. The reaction and the analytical separation are combined in a single experiment to investigate the Diels–Alder reaction of benzenediazonium-2-carboxylate as a benzyne precursor with various anthracene derivatives, i.e. anthracene, 9-bromoanthracene, 9-anthracenecarboxaldehyde and 9-anthracenemethanol. To overcome limitations of short reaction contact times at elevated temperatures a novel experimental setup was developed involving a cooling trap to achieve focusing and mixing of the reactants at a defined spot in a fused-silica capillary. This trap functions as a reactor within the separation column in the oven of a gas chromatograph. The reactants are sequentially injected to avoid undefined mixing in the injection port. An experimental protocol was developed with optimized injection intervals and cooling times to achieve sufficient conversions at short reaction times. Reaction products were rapidly identified by mass spectrometric detection. This new approach represents a practical procedure to investigate higher-order reactions at an analytical level and it simultaneously provides valuable information for the optimization of the reaction conditions.

Low-Temperature Experimental and Theoretical Rate Constants for the O(1D) + H2 Reaction.

Science.gov (United States)

Hickson, Kevin M; Suleimanov, Yury V

2017-03-09

In the present joint experimental and theoretical study, we report thermal rate constants for the O( 1 D) + H 2 reaction within the 50-300 K temperature range. Experimental kinetics measurements were performed using a continuous supersonic flow reactor coupled with pulsed laser photolysis for O( 1 D) production and pulsed laser-induced fluorescence in the vacuum ultraviolet wavelength range (VUV LIF) for O( 1 D) detection. Theoretical rate constants were obtained using the ring polymer molecular dynamics (RPMD) approach over the two lowest potential energy surfaces 1 1 A' and 1 1 A″, which possess barrierless and thermally activated energy profiles, respectively. Both the experimental and theoretical rate constants exhibit a weak temperature dependence. The theoretical results show the dominant role of the 1 1 A' ground state and that contribution of the 1 1 A″ excited state to the total thermal rate decreases dramatically at lower temperature. Agreement between the experimental and theoretical results is good, and the discrepancy does not exceed 25%. It is argued that these differences are likely to be due to nonadiabatic couplings between the 1 1 A' and 2 1 A' surfaces.

Experimental investigation of solid sodium-water reaction: tests results and phenomenological analysis

International Nuclear Information System (INIS)

Daudin, K.; Beauchamp, F.; Proust, C.

2014-01-01

Sodium-Water Reaction (SWR) is an issue one has to be capable to deal with for the next generation of nuclear reactors (SFR for GEN IV). The background of these experiments is the improvement of safety demonstration regarding SWR in an open volume. This experimental campaign is conducted at the CEA Cadarache inside a cylindrical reactor filled with inert gas. The sodium is inside a loading pot and water comes into contact by immersion. SWR and its physical effects are followed by different pressure and temperature sensors. The results show a limit to the overpressure increasing sodium mass. Global assessment of physical effects of SWR contributes to put forward the relative nature of phenomena with geometric configuration, and the importance of scale effects. (authors)

Reactions of stabilized Criegee Intermediates

Science.gov (United States)

Vereecken, Luc; Harder, Hartwig; Novelli, Anna

2014-05-01

Carbonyl oxides (Criegee intermediates) were proposed as key intermediates in the gas phase ozonolysis of alkenes in 1975 by Rudolf Criegee. Despite the importance of ozonolysis in atmospheric chemistry, direct observation of these intermediates remained elusive, with only indirect experimental evidence for their role in the oxidation of hydrocarbons, e.g. through scavenging experiments. Direct experimental observation of stabilized CI has only been achieved since 2008. Since then, a concerted effort using experimental and theoretical means is in motion to characterize the chemistry and kinetics of these reactive intermediates. We present the results of theoretical investigations of the chemistry of Criegee intermediates with a series of coreactants which may be of importance in the atmosphere, in experimental setups, or both. This includes the CI+CI cross-reaction, which proceeds with a rate coefficient near the collision limit and can be important in experimental conditions. The CI + alkene reactions show strong dependence of the rate coefficient depending on the coreactants, but is generally found to be rather slow. The CI + ozone reaction is sufficiently fast to occur both in experiment and the free troposphere, and acts as a sink for CI. The reaction of CI with hydroperoxides, ROOH, is complex, and leads both to the formation of oligomers, as to the formation of reactive etheroxides, with a moderately fast rate coefficient. The importance of these reactions is placed in the context of the reaction conditions in different atmospheric environments ranging from unpolluted to highly polluted.

A Kinetic Study of the Diels-Alder Reaction. An Experiment Illustrating Simple Second-Order Reaction Kinetics.

Science.gov (United States)

Silvestri, Michael G.; Dills, Charles E.

1989-01-01

Describes an organic chemistry experiment for teaching the basic concepts of chemical kinetics. Provides background information about first- and second-order reactions, experimental procedures of the Diels-Alder reaction between cyclopentadiene and dimethyl fumarate, and the experimental results. (YP)

The Inverse Demand Oxa-Diels-Alder Reaction of Resorcinarenes: An Experimental and Theoretical Analysis of Regioselectivity and Diastereoselectivity.

Science.gov (United States)

Stefańska, Karolina; Jędrzejewska, Hanna; Wierzbicki, Michał; Szumna, Agnieszka; Iwanek, Waldemar

2016-07-15

The Diels-Alder reaction enables introduction of new functionalities onto the resorcinarene skeleton with simultaneous generation of new stereogenic centers and expansion of the internal cavity. We present highly regio- and diastereoselective inverse electron demand oxa-Diels-Alder reactions of resorcinarene ortho-quinone methide with benzofuran and indene, each generating 12 new stereogenic centers. The mechanism and reasons for regioselectivity and diastereoselectivity were analyzed using theoretical calculations (NBO charges, Fukui functions, transition state energies, and thermodynamic stability of the products). Enantiomers were separated, and their configurations were determined by comparison of experimental and theoretical electronic circular dichroism spectra.

Synthesis and Characterization of Well-Defined Soluble Alq3- and Znq2-Functionalized Polymers via RAFT Copolymerization

Directory of Open Access Journals (Sweden)

Chengchao Wang

2010-01-01

Full Text Available The reversible addition-fragmentation chain transfer (RAFT copolymerizations of 2-((8-hydroxyquinolin-5-ylmethoxyethyl methacrylate (HQHEMA with styrene (St or methyl methacrylate (MMA were successfully carried out in the presence of 2-cyanoprop-2-yl dithionaphthalenoate (CPDN. The polymerization behaviors showed the typical living natures by the first-order polymerization kinetics, the linear dependence of molecular weights of the polymers on the monomer conversions with the relatively narrow molecular weight distributions (Mw/Mn, and the successful chain extension experiments. The soluble polymers having tris(8-hydroxyquinolinealuminum (Alq3 and bis(8-hydroxyquinoline znic(II (Znq2 side chains were obtained via complexation of the polymers with aluminium isopropoxide or zinc acetate in the presence of monomeric 8-hydroxyquinoline, which had strong fluorescent emission at 520 nm. The obtained polymers were characterized by GPC, NMR, UV-vis, and fluorescent spectra.

Experimental study of the attenuation waves oriented to transients caused by the sodium-water explosive reaction in fast reactors

International Nuclear Information System (INIS)

Pedroso, L.J.

1990-01-01

One of the problems related to fluid-structure interaction that can compromise the structural integrity of components of a fast reactor is the explosion caused by the sodium-water reaction, in the case of a flood at the level of the thermic exchange wall at the steam generator. In this paper we have considered the aspects of the pressure-waves damping caused by the reaction, when these waves transverse certain perforated structures. In order to solve this problem, we also adopted a parametric experimental approach, using a scale model (RIO test rig). (author)

An experimental study on impingement wastage of Mod 9Cr 1Mo steel due to sodium water reaction

Energy Technology Data Exchange (ETDEWEB)

Kishore, S., E-mail: skishore@igcar.gov.in [Fast Reactor Technology Group, Indira Gandhi Centre for Atomic Research, Kalpakkam (India); Ashok Kumar, A.; Chandramouli, S.; Nashine, B.K.; Rajan, K.K.; Kalyanasundaram, P.; Chetal, S.C. [Fast Reactor Technology Group, Indira Gandhi Centre for Atomic Research, Kalpakkam (India)

2012-02-15

Highlights: Black-Right-Pointing-Pointer Sodium heated steam generators are crucial components of fast breeder reactors. Black-Right-Pointing-Pointer A leak in steam generator tube will cause sodium water reaction that damages the tubes. Black-Right-Pointing-Pointer Experimental study was conducted to quantify the extent of damage on Mod 9Cr 1Mo tube due to a water leak. - Abstract: Sodium heated steam generator (SG) is a crucial component in the heat transport system of a fast breeder reactor (FBR). In case, one of its water/steam carrying tubes becomes defective, water/steam leaks into sodium, flowing in the shell side, causing sodium-water reaction, which is highly exothermic and producing corrosive NaOH. The reaction jet originating from a leaking tube may impinge on its adjacent tube, resulting in damage of the tube. Impingement wastage refers to this kind of damage, occurring to a tube of sodium heated SG, owing to a small water/steam leak from a neighboring tube. Extensive research works have been conducted all over the world to study various aspects of this phenomenon. Experimental studies were carried out in Indira Gandhi Centre for Atomic Research (IGCAR) to understand the effect of impingement wastage on Mod 9Cr 1Mo, which is the tube material of prototype fast breeder reactor (PFBR) SG. This paper brings out the data and experience gained through the experiments.

Multistep processes in nuclear reactions

International Nuclear Information System (INIS)

Hodgson, P.E.

1988-01-01

The theories of nuclear reactions are reviewed with particular attention to the recent work on multistep processes. The evidence for compound nucleus and direct interaction reactions is described together with the results of comparisons between theories and experimental data. These theories have now proved inadequate, and there is evidence for multistep processes that take place after the initial direct stage but long before the attainment of the statistical equilibrium characteristic of compound nucleus processes. The theories of these reactions are described and it is shown how they can account for the experimental data and thus give a comprehensive understanding of nuclear reactions. (author)

Reaction cross section calculation of some alkaline earth elements

Science.gov (United States)

Tel, Eyyup; Kavun, Yusuf; Sarpün, Ismail Hakki

2017-09-01

Reaction cross section knowledge is crucial to application nuclear physics such as medical imaging, radiation shielding and material evaluations. Nuclear reaction codes can be used if the experimental data are unavailable or are improbably to be produced because of the experimental trouble. In this study, there action cross sections of some target alkaline earth elements have been calculated by using pre-equilibrium and equilibrium nuclear reaction models for nucleon induced reactions. While these calculations, the Hybrid Model, the Geometry Dependent Hybrid Model, the Full Exciton Model, the Cascade Exciton Model for pre-equilibrium reactions and the Weisskopf-Ewing Model for equilibrium reactions have been used. The calculated cross sections have been discussed and compared with the experimental data taken from Experimental Nuclear Reaction Data library.

Exerting control over the helical chirality in the main chain of sergeants-and-soldiers-type poly(quinoxaline-2,3-diyl)s by changing from random to block copolymerization protocols.

Science.gov (United States)

Nagata, Yuuya; Nishikawa, Tsuyoshi; Suginome, Michinori

2015-04-01

Chiral random poly(quinoxaline-2,3-diyl) polymers of the sergeants-and-soldiers-type (sergeant units bearing (S)-3-octyloxymethyl groups) adopt an M- or P-helical conformation in the presence of achiral units bearing propoxymethyl or butoxy groups (soldier units), respectively. Unusual bidirectional induction of the helical sense can be observed for a copolymer with butoxy soldier units upon changing the mole fraction of the sergeant units. In the presence of 16-20% of sergeant units, the selective induction of a P-helix was observed, while the selective induction of an M-helix was observed for a mole fraction of sergeant units of more than 60%. This phenomenon could be successfully employed to control the helical chirality of copolymers by applying either random or block copolymerization protocols. Random or block copolymerization of sergeant and soldier monomers in a 18:82 ratio resulted in the formation of 250mers with almost absolute P- or M-helical conformation, respectively (>99% ee). Incorporation of a small amount of coordination sites into the random and block copolymers resulted in chiral macromolecular ligands, which allowed the enantioselective synthesis of both enantiomers in the Pd-catalyzed asymmetric hydrosilylation of β-methylstyrene.

Theoretical calculations of the reaction cross-sections for proton-induced reactions on natural copper using ALICE-IPPE code

International Nuclear Information System (INIS)

Alharbi, A.A.; Azzam, A.

2012-01-01

A theoretical study of the nuclear-reaction cross sections for proton-induced reactions on 63 Cu and 65 Cu was performed in the proton energy range from threshold values up to 50 MeV. The produced nuclei were different isotopes of Zn, Cu, Ni, Co and Mn, some of which have important applications. The reaction cross-section calculations were performed using the ALICE-IPPE code, which depends on the pre-equilibrium compound nucleus model. This code is suitable for the studied energy and isotopic mass ranges. Approximately 14 excitation functions for the different reactions have been constructed from the calculated cross-section values. The excitation function curves for the proton reactions with natural copper targets have been constructed from those for enriched targets using the natural abundance of the copper isotopes. Comparisons between the calculated excitation functions with those previously experimentally measured are given whenever the experimental values were available. Some statistical parameters were introduced to control the quality of the fitting between both the experimental and the theoretical calculated cross-section values. - Highlights: ► We performed reaction cross section calculations using ALICE-IPPE code. ► We constructed 14 excitation functions for nat Cu(p,xn)Zn,Cu,Ni,Co,Mn reactions. ► The available experimental data were fitted to the performed ALICE-IPPE calculations. ► Statistical parameters were introduced to control the quality of the fitting. ► The code failed to fit the experimental data for reactions with large nucleon emissions.

Experimental Guidance of ISB Corrections via Direct Nuclear Reactions

Science.gov (United States)

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.

An experimental study on sodium-water reaction in the double pool LMFBR, (4)

International Nuclear Information System (INIS)

Kumagai, Hiromichi; Yoshida, Kazuo; Uotani, Masaki; Akimoto, Tokuzo

1989-01-01

Double Pool type LMFBR set the rectangular cross-sectional steam generator (SGs) inside a secondary vessel. The initial spike pressure rise caused by large sodium-water reaction in SGs might be radiated into a large sodium pool in the secondary vessel. Therefore basic experiments on pressure wave propagation were carried out by generating pressure wave in water by mean of a set of drop hummer and piston. But the experimental apparatus in water was not convenience to simulate the structure near the bottom end of the SGs shell. In this reports, experiments were carried out by generating pulse sound pressure in air, and compared with the results pressure waves in water. (author)

Structure and thermal performance of poly(styrene-co-maleic anhydride)-g-alkyl alcohol comb-like copolymeric phase change materials

International Nuclear Information System (INIS)

Wang, Haixia; Shi, Haifeng; Qi, Miao; Zhang, Lingjian; Zhang, Xingxiang; Qi, Lu

2013-01-01

Graphical abstract: SMA-g-CnOH comb-like PCMs exhibit the better thermal stability against 1-alcohols due to the protection of SMA backbones, and the degradation temperature is dependent on the side-chain length, where at 5 wt% weight loss T d increased from 193 to 257 °C with n changing from 14 to 26. SMA-g-CnOH PCMs can be widely used under 300 °C for preparation of energy-saving products and materials. - Highlights: • The length of alkyl side-chains determines the thermal energy storage ability. • SMA backbone restricts the crystallization of alkyl side groups. • SMA-g-CnOH PCMs have the better thermal stability against 1-alcohols. - Abstract: A series of comb-like copolymeric phase change materials (SMA-g-CnOH) composed of poly(styrene-co-maleic anhydride) (SMA) and 1-alcohols CnOH with n = 14, 16, 18 or 26, respectively, was synthesized through grafting reaction. The structure and thermal properties of SMA-g-CnOH were investigated by 1 H nuclear magnetic resonance ( 1 H NMR), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and wide-angle X-ray diffraction (WAXD). The DSC analysis indicates that SMA-g-CnOH exhibit good structure stability with phase change enthalpies changing from 37.9 to 110.7 J g −1 . The results showed that the low thermal efficiency of SMA-g-CnOH was ascribed to the small CH 2 segments of side chains participating in the assembled structure of side-chain crystallites. Their advantageous structural stability and thermal performance of SMA-g-CnOH were favorable for phase change materials in the thermal energy storage systems. Additionally, the influence of side-chain length on thermal properties of SMA-g-CnOH also was discussed in detail in combination with the published results

Reaction cross section calculation of some alkaline earth elements

Directory of Open Access Journals (Sweden)

Tel Eyyup

2017-01-01

Full Text Available Reaction cross section knowledge is crucial to application nuclear physics such as medical imaging, radiation shielding and material evaluations. Nuclear reaction codes can be used if the experimental data are unavailable or are improbably to be produced because of the experimental trouble. In this study, there action cross sections of some target alkaline earth elements have been calculated by using pre-equilibrium and equilibrium nuclear reaction models for nucleon induced reactions. While these calculations, the Hybrid Model, the Geometry Dependent Hybrid Model, the Full Exciton Model, the Cascade Exciton Model for pre-equilibrium reactions and the Weisskopf-Ewing Model for equilibrium reactions have been used. The calculated cross sections have been discussed and compared with the experimental data taken from Experimental Nuclear Reaction Data library.

Synthesis of nano-sized stereoselective imprinted polymer by copolymerization of (S)-2-(acrylamido) propanoic acid and ethylene glycol dimethacrylate in the presence of racemic propranolol and copper ion

Energy Technology Data Exchange (ETDEWEB)

Alizadeh, Taher, E-mail: talizadeh@ut.ac.ir [Department of Analytical Chemistry, Faculty of Chemistry, University College of Science, University of Tehran, P.O. Box 14155-6455, Tehran (Iran, Islamic Republic of); Bagherzadeh, Azam; Shamkhali, Amir Nasser [Department of Applied Chemistry, Faculty of Science, University of Mohaghegh Ardabili, Ardabil (Iran, Islamic Republic of)

2016-06-01

A new chiral functional monomer of (S)-2-(acrylamido) propanoic acid was obtained by reaction of (L)-alanine with acryloyl chloride. The resulting monomer was characterized by FT-IR and HNMR and then utilized for the preparation of chiral imprinted polymer (CIP). This was carried out by copolymerization of (L)-alanine-derived chiral monomer and ethylene glycol dimethacrylate, in the presence of racemic propranolol and copper nitrate, via precipitation polymerization technique, resulting in nano-sized networked polymer particles. The polymer obtained was characterized by scanning electron microscopy and FT-IR. The non-imprinted polymer was also synthesized and used as blank polymer. Density functional theory (DFT) was also employed to optimize the structures of two diasterometric ternary complexes, suspected to be created in the pre-polymerization step, by reaction of optically active isomers of propranolol, copper ion and (S)-2-(acrylamido) propanoic acid. Relative energies and other characteristics of the described complexes, calculated by the DFT, predicted the higher stability of (S)-propranolol involved complex, compared to (R)-propranolol participated complex. Practical batch extraction test which employed CIP as solid phase adsorbent, indicated that the CIP recognized selectively (S)-propranolol in the racemic mixture of propranolol; whereas, the non-imprinted polymer (NIP) showed no differentiation capability between two optically active isomers of propranolol. - Highlights: • A new chiral functional monomer of (S)-2-(acrylamido) propanoic acid was synthesized. • (S)-propranolol-selective imprinted polymer was synthesized using the chiral monomer. • Racemic propranolol mixed with Cu(II) was used as template in the imprinting. • Density functional theory was employed to clarify the imprinting mechanism. • (S)-propranolol-Cu(II) complex was shown to conduct the imprinting process.

Theoretical and experimental cross sections for neutron reactions on 64Zinc

International Nuclear Information System (INIS)

Rutherford, D.A.

1987-01-01

Accurate measurements of the 64 Zn (n,2n) 64 Cu and 64 Zn (n,p) 63 Zn cross sections at 14.8 MeV have been made using a Texas Nuclear Neutron Generator and the activation technique. A NaI(T1) spectrometer (using two 6'' x 6'' NaI detectors/crystals) was used to measure the gamma radiation emitted in coincidence from the positron-emitting decay products. The measurements were made relative to 65 Cu (n,2n) /64/Cu and 63 Cu (n,2n) 62 Cu cross sections, which have similar half-lives, radiation emission, and were previously measured to high accuracy (2 percent). The value obtained for the (n,2n) measurement was 199 /+-/ 6 millibarns, and a value of 176 /+-/ 4.5 millibarns was obtained for the (n,p) measurement. In concert, a theoretical analysis of neutron induced reactions on /64/Zn was performed at Los Alamos National Laboratory using the Hauser-Feshbach statistical theory in the GNASH code over an energy range of 100 keV to 20 MeV. Calculations included width fluctuation corrections, direct reaction contributions, and preequilibrium corrections above 6 MeV. Neutron optical model potentials were determined for zinc. The theoretical values agree with the new 14.8 MeV measurements approximately within experimental error, with calculations of 201 millibarns for the (n,2n) cross section and 170 millibarns for the (n,p) cross section. Results from the analysis will be made available in National Evaluated Nuclear Data Format (ENDF/B) for fusion energy applications. 50 refs., 34 figs., 10 tabs

Chemical transport reactions

CERN Document Server

Schäfer, Harald

2013-01-01

Chemical Transport Reactions focuses on the processes and reactions involved in the transport of solid or liquid substances to form vapor phase reaction products. The publication first offers information on experimental and theoretical principles and the transport of solid substances and its special applications. Discussions focus on calculation of the transport effect of heterogeneous equilibria for a gas motion between equilibrium spaces; transport effect and the thermodynamic quantities of the transport reaction; separation and purification of substances by means of material transport; and

Experimental and theoretical investigations on safety of the SNR - straight-tube design steam generator with sodium-water reactions

International Nuclear Information System (INIS)

Dumm, K.; Sauermann, F.; Schnitker, W.; Welter, A.

A number of large sodium-water reaction tests has been performed in a steam generator model in order to verify the layout criteria of the SNR straight-tube design steam generators under accident conditions. The experimental setup is described. The test results and their applicability to the SNR steam generators are given and discussed. (U.S.)

Singlet oxygen reactions with flavonoids. A theoretical-experimental study.

Science.gov (United States)

Morales, Javier; Günther, Germán; Zanocco, Antonio L; Lemp, Else

2012-01-01

Detection of singlet oxygen emission, λ(max) = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, k(T), and the reactive reaction rate constant, k(r), for the reaction between singlet oxygen and several flavonoids. Values of k(T) determined in deuterated water, ranging from 2.4×10(7) M(-1) s(-1) to 13.4×10(7) M(-1) s(-1), for rutin and morin, respectively, and the values measured for k(r), ranging from 2.8×10(5) M(-1) s(-1) to 65.7×10(5) M(-1) s(-1) for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid.

Singlet oxygen reactions with flavonoids. A theoretical-experimental study.

Directory of Open Access Journals (Sweden)

Javier Morales

Full Text Available Detection of singlet oxygen emission, λ(max = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, k(T, and the reactive reaction rate constant, k(r, for the reaction between singlet oxygen and several flavonoids. Values of k(T determined in deuterated water, ranging from 2.4×10(7 M(-1 s(-1 to 13.4×10(7 M(-1 s(-1, for rutin and morin, respectively, and the values measured for k(r, ranging from 2.8×10(5 M(-1 s(-1 to 65.7×10(5 M(-1 s(-1 for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid.

Radiation-induced synthesis and swelling properties of p(2-hydroxyethyl methacrylate-co-itaconic acid-co-oligo(ethylene glycol) acrylate) copolymeric hydrogels

International Nuclear Information System (INIS)

Micic, M.; Suljovrujic, E.

2011-01-01

Complete text of publication follows. Since it is presumed that by incorporation of pH-responsive (IA) and temperature-responsive (OEGA) co-monomers it is possible to prepare P(HEMA-co-IA-co-OEGA) hydrogels with duel (pH and thermo) responsiveness, the main purpose of this paper is to investigate the influence of different mole fractions of IA and especially OEGA on the diversity of the swelling properties of obtained hydrogels. For that reason, a series of copolymeric hydrogels with different mole ratios of 2-hydroxyethyl methacrylate (HEMA), itaconic acid (IA) and oligo(ethylene glycol) acrylates (OEGA) was synthesized by gamma radiation. The obtained hydrogels were characterized by swelling studies in the wide pH (2.2-9.0) and temperature range (25-70 deg C), confirming dual (pH and thermo) responsiveness and a large variation in swelling capability. It was observed that the equilibrium swelling of P(HEMA-co-IA-co-OEGA) hydrogels, for a constant amount of IA, increases progressively with increasing in OEGA share. On the other hand, the dissociation of carboxyl (-COOH) groups from IA occurs at pH > 4; therefore, small mole fractions of IA render good pH sensitivity and a large increase in the swelling capacity of these hydrogels at higher pH values. Additional characterization of structure and properties was conducted by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and mechanical measurements, confirming that the inherent properties of the P(HEMA-co-IA-co-OEGA) hydrogels can be significantly tuned by variation in their composition. According to all presented, it seems that the obtained copolymeric hydrogels can be a beneficial synergetic combination for controlled delivery of bioactive molecules such as drugs, nucleic acids, peptides, and proteins.

Study on reactive extrusion processes of block copolymer

International Nuclear Information System (INIS)

Wu Lili; Jia Yuxi; Sun Sheng; Zhang Guofang; Zhao Guoqun; An Lijia

2007-01-01

The anionic copolymerization process of styrene-butadiene (S/B) block copolymer in a closely intermeshing co-rotating twin screw extruder with butyl-lithium initiator was studied. According to the anionic copolymerization mechanism and the reactive extrusion characteristics, the mathematical models of monomer conversion, average molecular weight and fluid viscosity during the anionic copolymerization of S/B were constructed, and then the reactive extrusion process was simulated by means of the finite volume method and the uncoupled semi-implicit iterative algorithm. Finally, the influence of the feeding mixture composition on conversion was discussed. The simulated results were nearly in agreement with the experimental results

Stereoselective Copolymerization of Styrene with Terpenes Catalyzed by an Ansa-Lanthanidocene Catalyst: Access to New Syndiotactic Polystyrene-Based Materials

Directory of Open Access Journals (Sweden)

Eva Laur

2017-11-01

Full Text Available The copolymerization of bio-renewable β-myrcene or β-farnesene with styrene was examined using an ansa-neodymocene catalyst, affording two series of copolymers with high styrene content and unprecedented syndioregularity of the polystyrene sequences. The incorporation of terpene in the copolymers ranged from 5.6 to 30.8 mol % (β-myrcene and from 2.5 to 9.8 mol % (β-farnesene, respectively. NMR spectroscopy and DSC analyses suggested that the microstructure of the copolymers consists of 1,4- and 3,4-poly(terpene units randomly distributed along syndiotactic polystyrene chains. The thermal properties of the copolymers are strongly dependent on the terpene content, which is easily controlled by the initial feed. The terpolymerization of styrene with β-myrcene in the presence of ethylene was also examined.

Methyl Methacrylate and Alpha-Methyl Styrene: New Strategy for Synthesis of Bloc Copolymers for Use in Potential Biomedical Applications Generated by an Ecologic Catalyst Called Maghnite (Algerian MMT

Directory of Open Access Journals (Sweden)

Moulkheir Ayat

2016-10-01

Full Text Available A new model for synthesis of the plastics, block copolymers were prepared from methyl methacrylate (MMA and alpha-methyl styrene (α-MS by cationic copolymerization in the presence of a new and efficient catalyst of “Maghnite-Na” at 0 °C in bulk. In this paper, the copolymerization of α-MS and MMA was induced in heterogeneous phase catalyzed by Maghnite-Na was investigated under suitable conditions. The “Maghnite-Na” is a montmorillonite sheet silicate clay, with exchanged sodium cations to produce Na-Montmorillonite (Na+-MMT obtained from Tlemcen, Algeria, was investigated to remove heavy metal ion from wastewater as an efficient catalyst for cationic polymerization of many vinylic and heterocyclic monomers. The synthesized copolymer were characterized by Nuclear Magnetic Resonance (NMR-1H, NMR-13C, FT-IR spectroscopy, Differential Scanning Calorimetry (DSC, and Gel Permeation Chromatography (GPC to elucidate structural characteristics and thermal properties of the resulting copolymers. The structure compositions of “MMT”, “H+-MMT” and “Na+-MMT” have been developed. The effect of the MMA/α-MS molar ratio on the rate of copolymerization, the amount of catalyst, temperature and time of copolymerization on yield of copolymers was studied. The yield of copolymerization depends on the amount of Na+-MMT used and the reaction time. The kinetic studies indicated that the polymerization rate is first order with respect to monomer concentration. A possible mechanism of this cationic polymerization is discussed based on the results of the 1H-NMR Spectroscopic analysis of these model reactions. A cationic mechanism for the reaction studies showed that monomer was inserted into the growing chains. Copyright © 2016 BCREC GROUP. All rights reserved Received: 2nd May 2015; Revised: 24th February 2016; Accepted: 15th March 2016 How to Cite: Ayat, M., Belbachir, M., Rahmouni, A. (2016. Methyl Methacrylate and Alpha-Methyl Styrene: New

Solar nuclear reactions

Energy Technology Data Exchange (ETDEWEB)

Kocharov, G

1978-04-01

The current state of neutrino solar astrophysics is outlined, showing the contradictions between the experimental results of solar neutrino detection and the standard solar models constructed on the basis of the star structure and development theory, which give values for high-energy neutrino fluxes considerably exceeding the upper experimental limit. A number of hypotheses interpreting the experimental results are summarized. The hypotheses are critically assessed and experiments are recommended for refining or verifying experimental data. Also dealt with are nuclear reactions in the Sun, as is the attempt to interpret the anomalous by high /sup 3/He fluxes from the Sun and the relatively small amounts of solar neutrinos and gamma quanta. The importance is emphasized of the simultaneous and complex measurement of the fluxes of neutrons, gamma radiation, and isotopes of hydrogen, helium, and boron from the Sun as indicators of nuclear reactions in the Sun.

Investigation of Na-CO2 Reaction with Initial Reaction in Various Reacting Surface

International Nuclear Information System (INIS)

Kim, Hyun Su; Park, Gunyeop; Kim, Soo Jae; Park, Hyun Sun; Kim, Moo Hwan; Wi, Myung-Hwan

2015-01-01

The reaction products that cause oxidation and erosion are threaten the heat transfer tubes so that it is necessary to investigate Na-CO 2 reaction according to various experimental parameter. Unlike SWR, Na-CO 2 reaction is more complex to deal with reaction kinetics. Since a comprehensive understanding of Na-CO 2 reaction mechanism is crucial for the safety analysis, the reaction phenomenon under the various conditions was investigated. The current issue is to make a database for developing computational code for CO 2 gas leak situation because it is experimentally difficult to analyze the actual accident situation. Most studies on Na-CO 2 interaction reports that chemical reaction is getting vigorous as temperature increased and reactivity is sensitive as temperature change between 400 .deg. C and 600 .deg. C. Therefore, temperature range is determined based on the operating condition (450 - 500 .deg. C) of KALIMER-600 employed as supercritical CO 2 brayton cycle energy conversion system for Na-CO 2 heat exchanger. And next parameter is sodium surface area which contact between sodium and CO 2 when CO 2 is injected into sodium pool in the accident situation. So, the fundamental surface reaction is experimentally studied in the range of 8 - 12cm 2 . Additionally, it has been reported in recent years that CO 2 Flow rate affects reactivity less significantly and CO 2 flow rate is assumed that 5 SLPM (standard liter per minute) is suitable as a basis for a small leakage. The finally selected control parameters is sodium temperature and reacting surface area with constant CO 2 flow rate. Na-CO 2 reaction test is performed for investigating risk of potential accident which contacts with liquid sodium and CO 2 . Amount of reaction is saturated as time passed because of kept a balance between production of solid phase reaction products and amount of diffusivity. These results contribute to make a database for the SFR safety analysis and additional experiments are needed

Modification on liquid retention property of cassava starch by radiation grafting with acrylonitrile: Pt. 1

International Nuclear Information System (INIS)

Kiatkamjornwong, S.; Nakason, C.; Chvajarempun, J.

1993-01-01

Radiation modification on liquid retention properties of native cassava starch, gelatinized at 85 o C, by graft copolymerization with acrylonitrile was carried out by mutual irradiation to gamma-rays. A thin aluminium foil was used to cover the inner wall of the reaction vessel, so that the homopolymer concentration was reduced to be less than 1.0% with a distilled water retention value of 665 g/g of the dry weight of the saponified grafted product. Confirmation of graft copolymerization and saponification reactions was made by the infrared spectrophotometric technique. The combined effect of radiation parameters in terms of an irradiation time and a dose rate to the total dose on the extent of the grafting reaction expressed in terms of grafting parameters which directly influenced liquid retention values was evaluated in conjunction with statistical analysis. (author)

Effect of gamma rays on grafting parameters and liquid retention property of cassava starch-g-PAN

International Nuclear Information System (INIS)

Kiatkamjornwong, S.; Chvajarernpun, J.; Nakason, C.

1992-01-01

Radiation modification on liquid retention properties of native cassava starch, gelatinized at 85 0 C, by graft copolymerization with acrylonitrile was carried out by mutual irradiation to γ-rays. A thin aluminium foil was used to cover the inner wall of the reaction vessel so that the extent of homo polymer could be reduced to be less than 1.6% with a distilled water retention value of 665 g/g of the dry weight of the saponified grafted product. Confirmations of graft copolymerization and saponification reactions were made by the infrared spectrophotometric technique. The combined effect of radiation parameters in terms of an irradiation time and a dose rate to the same total dose on the extent of grafting reaction expressed in terms of grafting parameters which directly influenced liquid retention values was evaluated in conjunction with statistical analysis

Sequential charged particle reaction

International Nuclear Information System (INIS)

Hori, Jun-ichi; Ochiai, Kentaro; Sato, Satoshi; Yamauchi, Michinori; Nishitani, Takeo

2004-01-01

The effective cross sections for producing the sequential reaction products in F82H, pure vanadium and LiF with respect to the 14.9-MeV neutron were obtained and compared with the estimation ones. Since the sequential reactions depend on the secondary charged particles behavior, the effective cross sections are corresponding to the target nuclei and the material composition. The effective cross sections were also estimated by using the EAF-libraries and compared with the experimental ones. There were large discrepancies between estimated and experimental values. Additionally, we showed the contribution of the sequential reaction on the induced activity and dose rate in the boundary region with water. From the present study, it has been clarified that the sequential reactions are of great importance to evaluate the dose rates around the surface of cooling pipe and the activated corrosion products. (author)

A study on sodium-concrete reaction

Energy Technology Data Exchange (ETDEWEB)

Bae, Jae Heum; Min, Byong Hun [Suwon University, Suwon (Korea, Republic of)

1997-07-01

A small sodium-concrete reaction facility was designed, manufactured and installed. this facility has been operated under inert gas(N{sub 2}) with different experimental variables such as sodium injection temperature, injection amount of sodium, aging period of concrete, sodium reservoir temperature. As a result, it was found that sodium injection temperature and injected amount of sodium has little effect on sodium-concrete reaction. However, sodium reservoir temperature and aging period of concrete has relatively high impact on sodium-concrete reaction. Sodium-concrete reaction model has also been developed and compared with experimental results. (Author) 51 refs., 16 tabs., 64 figs.

The mechanisms of the hadron-nucleus collision processes and of the hadron-nucleus collision induced nuclear reactions - in the light of experimental data

International Nuclear Information System (INIS)

Strugalski, Z.; Strugalska-Gola, E.

1997-01-01

The mechanisms of the hadron-nucleus collision processes and of the hadron-nucleus collision induced nuclear reactions are described - as experimentally based. The target nuclei are damaged definitely and locally in the collisions and the configurations of the nucleons in them became instable. The configuration must transit into stable stages of the nuclear transition reaction products. The difference between the initial internal energy of the unstable residual nucleus and the total final energy of the stable products of the nuclear transition reaction may be released in some cases

Computational and experimental studies on stabilities, reactions and reaction rates of cations and ion-dipole complexes

NARCIS (Netherlands)

Ervasti, H.K.

2008-01-01

In this thesis, ion stability, ion-molecule reactions and reaction rates are studied using mass spectrometry and molecular modelling. In Chapter 2 the effect of functional group substitution on neutral and ionised ketene are studied. Electron-donating substituents show a stabilising positive

Role of deep inelastic processes in nuclear physics: experimental and theoretical aspects of deep inelastic reactions

International Nuclear Information System (INIS)

Moretto, L.G.

1979-03-01

The collective modes excited in deep-inelastic reactions and their natural hierarchy provided by their characteristic relaxation times is described. The relaxation of the mass asymmetry mode is discussed in terms of a diffusion process. Charge distributions and angular distributions as a function of Z calculated with this model are in good agreement with experimental data. This diffusion model also treats the transfer of energy and angular momentum in terms of particle transfer, and is successfully compared with experimental γ-ray multiplicities as a function of both Q-value and mass asymmetry. The angular momentum transfer is again considered in connection with the sequential fission of heavy, deep-inelastic fragments and the excitation of collective modes in the exit channel is considered. The role of the giant E1 mode in the equilibration of the neutron-to-proton ratio is discussed. 39 references

Heavy ion reactions: an experimental vista

International Nuclear Information System (INIS)

Stokstad, R.G.

1977-01-01

Examples of recent experiments in the areas of fusion and deep-inelastic scattering are presented and discussed. Emphasis is placed on the importance of individual nucleons in the fusion process, the effects of high angular momentum, and the understanding of compound nuclear decay. Experiments on deep inelastic scattering are entering a new stage in which important parameters of the reaction mechanism are now open to investigation. Primarily through coincidence measurements, direct information on the angular momentum transferred in a collision and on the time scale of decay is being obtained

Luminescent sensitization and blue shift emission of Ir(ppy){sub 2}(VPHD) by copolymerization with MMA

Energy Technology Data Exchange (ETDEWEB)

An Baoli, E-mail: blan@staff.shu.edu.cn [Department of Chemistry, College of Science, Shanghai University, Shanghai 200444 (China); Dai Fanzeng; Zhang Yanling; Song Jian; Huang, Xiao-Di [Department of Chemistry, College of Science, Shanghai University, Shanghai 200444 (China); Xu, Jia-Qiang, E-mail: xujiaqiang@shu.edu.cn [Department of Chemistry, College of Science, Shanghai University, Shanghai 200444 (China); State Key Laboratory of Transducer Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 (China)

2011-08-15

Ir(ppy){sub 2}(VPHD) (ppy=2-phenyl pyridine, VPHD=6-(4-vinylphenyl)-2,4-hexanedione) was copolymerized with methyl methacrylate (MMA). The copolymer had high quantum yield of 52.3{+-}0.5% in dilute ethyl acetate solution, and the yield increased around 45% than that of the iridium monomer. The maximum emission peaks for the copolymers shifted from 515 to 489 nm while the iridium complex content was less than 0.005 mol% in the feed. The blue emission at 489 nm and the green emission at 520 nm were analyzed by Lorenz function. They are attributed to {sup 1}MLCT and {sup 3}MLCT emissions, respectively. - Highlights: > PMMA-Ir(ppy){sub 2}(VPHD) as luminescent material with high yield of 53%. > The blue color emission at 489 nm from {sup 1}MLCT in conformity with Lorenz function. > The quantum yield for the copolymer increases 45% than that of the iridium monomer. > The {sup 3}MLCT Ex. intensity versus the monomer concentration is in conformity with Boltzmann function.

Chemical kinetics of gas reactions

CERN Document Server

Kondrat'Ev, V N

2013-01-01

Chemical Kinetics of Gas Reactions explores the advances in gas kinetics and thermal, photochemical, electrical discharge, and radiation chemical reactions. This book is composed of 10 chapters, and begins with the presentation of general kinetic rules for simple and complex chemical reactions. The next chapters deal with the experimental methods for evaluating chemical reaction mechanisms and some theories of elementary chemical processes. These topics are followed by discussions on certain class of chemical reactions, including unimolecular, bimolecular, and termolecular reactions. The rema

Experimental and theoretical study of the reactions between neutral vanadium oxide clusters and ethane, ethylene, and acetylene.

Science.gov (United States)

Dong, Feng; Heinbuch, Scott; Xie, Yan; Rocca, Jorge J; Bernstein, Elliot R; Wang, Zhe-Chen; Deng, Ke; He, Sheng-Gui

2008-02-13

Reactions of neutral vanadium oxide clusters with small hydrocarbons, namely C2H6, C2H4, and C2H2, are investigated by experiment and density functional theory (DFT) calculations. Single photon ionization through extreme ultraviolet (EUV, 46.9 nm, 26.5 eV) and vacuum ultraviolet (VUV, 118 nm, 10.5 eV) lasers is used to detect neutral cluster distributions and reaction products. The most stable vanadium oxide clusters VO2, V2O5, V3O7, V4O10, etc. tend to associate with C2H4 generating products V(m)O(n)C2H4. Oxygen-rich clusters VO3(V2O5)(n=0,1,2...), (e.g., VO3, V3O8, and V5O13) react with C2H4 molecules to cause a cleavage of the C=C bond of C2H4 to produce (V2O5)(n)VO2CH2 clusters. For the reactions of vanadium oxide clusters (V(m)O(n)) with C2H2 molecules, V(m)O(n)C2H2 are assigned as the major products of the association reactions. Additionally, a dehydration reaction for VO3 + C2H2 to produce VO2C2 is also identified. C2H6 molecules are quite stable toward reaction with neutral vanadium oxide clusters. Density functional theory calculations are employed to investigate association reactions for V2O5 + C2H(x). The observed relative reactivity of C2 hydrocarbons toward neutral vanadium oxide clusters is well interpreted by using the DFT calculated binding energies. DFT calculations of the pathways for VO3+C2H4 and VO3+C2H2 reaction systems indicate that the reactions VO3+C2H4 --> VO2CH2 + H2CO and VO3+C2H2 --> VO2C2 + H2O are thermodynamically favorable and overall barrierless at room temperature, in good agreement with the experimental observations.

Charge state distribution of 16O from the 4He(12C,16O)γ reaction of astrophysical interest studied both experimentally and theoretically

International Nuclear Information System (INIS)

Liu, Shengjin; Sakurai, Makoto; Sagara, Kenshi; Teranishi, Takashi; Fujita, Kunihiro; Yamaguchi, Hiroyuki; Matsuda, Sayaka; Mitsuzumi, Tatsuki; Iwazaki, Makoto; Rosary, Mariya T.; Kato, Daiji; Tolstikhina, I.Yu.

2014-01-01

In astrophysics, 4 He( 12 C, 16 O)γ reaction places an important role. At Kyushu University Tandem accelerator Laboratory (KUTL), the measurement of 4 He( 12 C, 16 O)γ cross section is in progress in the energy range of astrophysical nuclear reaction. Since the charge state of product 16 O ions after passing through the gas target is spread and only one charge state can be measured at terminal detector, it is necessary to know the charge state distribution of 16 O ions passing through the He gas target precisely. Here, we report the charge state distribution of the 16 O recoils both experimentally and theoretically. Experimentally, we measured the equilibrium charge state distribution of 16 O ions in the windowless helium gas target with the beam energy of primary 16 O ions at 7.2, 4.5, and 3.45 MeV at KUTL. The measured results showed a Gaussian distribution for the charge state fraction. Theoretically, we proposed a framework for the charge state distribution study. Charge state distribution was computed by solving a set of differential equations including a series of charge exchange cross sections. For the ionization cross section, plane-wave Born approximation was applied and modified by taking target atomic screening as a function of momentum transfer into account. For the capture cross section, continuum distorted wave approximation was applied and the influence of the gas target density was taken into account in the process of electron capture. Using above charge exchange cross sections, the charge state evolution was simulated. According to the equilibrium distribution, we compared the theoretical calculation to the experimental data. After taking into account the density effects in the charge exchange process, the theoretical charge state distributions shows a good agreement with the experimental data. Both experimental and theoretical results are useful to understand the charge fraction of recoil oxygen created via 4 He( 12 C, 16 O)γ reaction

Arabidopsis peroxidase-catalyzed copolymerization of coniferyl and sinapyl alcohols: kinetics of an endwise process.

Science.gov (United States)

Demont-Caulet, Nathalie; Lapierre, Catherine; Jouanin, Lise; Baumberger, Stéphanie; Méchin, Valérie

2010-10-01

In order to determine the mechanism of the earlier copolymerization steps of two main lignin precursors, sinapyl (S) alcohol and coniferyl (G) alcohol, microscale in vitro oxidations were carried out with a PRX34 Arabidopsis thaliana peroxidase in the presence of H(2)O(2). This plant peroxidase was found to have an in vitro polymerization activity similar to the commonly used horseradish peroxidase. The selected polymerization conditions lead to a bulk polymerization mechanism when G alcohol was the only phenolic substrate available. In the same conditions, the presence of S alcohol at a 50/50 S/G molar ratio turned this bulk mechanism into an endwise one. A kinetics monitoring (size-exclusion chromatography and liquid chromatography-mass spectrometry) of the different species formed during the first 24h oxidation of the S/G mixture allowed sequencing the bondings responsible for oligomerization. Whereas G homodimers and GS heterodimers exhibit low reactivity, the SS pinoresinol structure act as a nucleating site of the polymerization through an endwise process. This study is particularly relevant to understand the impact of S units on lignin structure in plants and to identify the key step at which this structure is programmed. Copyright © 2010 Elsevier Ltd. All rights reserved.

Synthesis and characterization of high molecular weight hydrophobically modified polyacrylamide nanolatexes using novel nonionic polymerizable surfactants

Directory of Open Access Journals (Sweden)

A.M. Al-Sabagh

2013-12-01

Full Text Available In this article, nine hydrophobically modified polyacrylamides (HM-PAM nanolatexes, were synthesized by copolymerizing the acrylamide monomer and novel polymerizable surfactants (surfmers. The reaction was carried out by inverse microemulsion copolymerization technique. The copolymerization was initiated by redox initiators composed of potassium peroxodisulphate and sodium bisulfite. The emulsion was stabilized using mixed tween 85 and span 80 as nonionic emulsifiers. The prepared HM-PAMs were classified into three groups according to the surfmers used in the copolymerization. The chemical structures of the prepared HM-PAMs were confirmed by FT-IR, 1H NMR and 13C NMR. The thermal properties were estimated with the thermal gravimetric analysis (TGA. The size and morphology of the prepared latexes were investigated by the dynamic light scattering (DLS and the High Resolution Transmission Electron Microscope (HRTEM. Finally, the molecular weights of the prepared copolymers were determined by the GPC and the viscosity average molecular weight method. They were situated between 1.58 × 106 and 0.89 × 106.

Zirconium and Yttrium (p, d) Surrogate Nuclear Reactions: Measurement and determination of gamma-ray probabilities: Experimental Physics Report

Energy Technology Data Exchange (ETDEWEB)

Burke, J. T. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Hughes, R. O. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Escher, J. E. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Scielzo, N. D. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Casperson, R. J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Ressler, J. J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Saastamoinen, A. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Ota, S. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Park, H. I. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Ross, T. J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); McCleskey, M. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); McCleskey, E. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Austin, R. E. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Rapisarda, G. G. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

2017-09-21

This technical report documents the surrogate reaction method and experimental results used to determine the desired neutron induced cross sections of ⁸⁷Y(n,g) and the known ⁹⁰Zr(n,g) cross section. This experiment was performed at the STARLiTeR apparatus located at Texas A&M Cyclotron Institute using the K150 Cyclotron which produced a 28.56 MeV proton beam. The proton beam impinged on Y and Zr targets to produce the nuclear reactions ⁸⁹Y(p,d)⁸⁸Y and ⁹²Zr(p,d)⁹¹Zr. Both particle singles data and particle-gamma ray coincident data were measured during the experiment. This data was used to determine the γ-ray probability as a function of energy for these reactions. The results for the γ-ray probabilities as a function of energy for both these nuclei are documented here. For completeness, extensive tabulated and graphical results are provided in the appendices.

Singlet Oxygen Reactions with Flavonoids. A Theoretical – Experimental Study

Science.gov (United States)

Morales, Javier; Günther, Germán; Zanocco, Antonio L.; Lemp, Else

2012-01-01

Detection of singlet oxygen emission, λmax = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, kT, and the reactive reaction rate constant, kr, for the reaction between singlet oxygen and several flavonoids. Values of kT determined in deuterated water, ranging from 2.4×107 M−1s−1 to 13.4×107 M−1s−1, for rutin and morin, respectively, and the values measured for kr, ranging from 2.8×105 M−1s−1 to 65.7×105 M−1s−1 for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid. PMID:22802966

Studies in the reaction dynamics of beam-gas chemiluminescent reactions

International Nuclear Information System (INIS)

Prisant, M.G.

1984-01-01

This thesis develops techniques for the analysis and interpretation of data obtained from beam-gas chemiluminescence experiments. These techniques are applied to experimental studies of atom transfer reactions of the type A + BC → AB + C. A procedure is developed for determining the product rotational alignment in the center-of-mass frame from polarization measurements of chemiluminescent atom-diatom exchange reactions under beam-gas conditions. Knowledge of a vector property of a reaction, such as product alignment, provides information on the disposition of angular momentum by a chemical reaction. Fluorescence polarization and hence product alignment are measured for two prototype reactions. The reaction of metastable calcium atoms with hydrogen-chloride gas yields highly aligned calcium-chloride product which exhibits little variation of alignment with vibrational state. The reaction of ground-state calcium with fluorine gas yields moderately aligned product which shows strong variation of alignment with vibration. A multi-surface direct-interaction model is developed to interpret product alignment and population data. The predictions of this model for the reaction of calcium with fluorine show reasonable agreement with experiment

Soft-to-hard templating to well-dispersed N-doped mesoporous carbon nanospheres via one-pot carbon/silica source copolymerization

Institute of Scientific and Technical Information of China (English)

Qinglu Kong; Lingxia Zhang; Min Wang; Mengli Li; Heliang Yao; Jianlin Shi

2016-01-01

Here we report a new approach referred as "softto-hard templating" strategy via the copolymerization of carbon source (dopamine) and silica source (tetraethyl orthosilicate) for the synthesis of well dispersed N-doped mesoporous carbon nanospheres (MCNs),which exhibit high performance for electrochemical supercapacitor.This method overcomes the shortcoming of uncontrolled dispersity and complicated procedures of soft-or hard-tem-plating methods,respectively.Moreover,the synthesized MCNs feature enriched heteroatom N-doping and easy functionalization by noble-metal nanoparticles during the one-pot synthesis.All the above characters make the asprepared MCNs a promising platform in a variety of applications.To demonstrate the applicability of the synthesized nitrogen-doped MCNs,this material has been employed as an electrode for high-performance electrochemical supercapacitor,which shows a capacitance of 223 and 140 F/g at current densities of 0.5 and 10 A/g in 1 mol/L KOH electrolyte,respectively.

Design of a single-step immunoassay principle based on the combination of an enzyme-labeled antibody release coating and a hydrogel copolymerized with a fluorescent enzyme substrate in a microfluidic capillary device.

Science.gov (United States)

Wakayama, Hideki; Henares, Terence G; Jigawa, Kaede; Funano, Shun-ichi; Sueyoshi, Kenji; Endo, Tatsuro; Hisamoto, Hideaki

2013-11-21

A combination of an enzyme-labeled antibody release coating and a novel fluorescent enzyme substrate-copolymerized hydrogel in a microchannel for a single-step, no-wash microfluidic immunoassay is demonstrated. This hydrogel discriminates the free enzyme-conjugated antibody from an antigen-enzyme-conjugated antibody immunocomplex based on the difference in molecular size. A selective and sensitive immunoassay, with 10-1000 ng mL(-1) linear range, is reported.

Structure and thermal performance of poly(styrene-co-maleic anhydride)-g-alkyl alcohol comb-like copolymeric phase change materials

Energy Technology Data Exchange (ETDEWEB)

Wang, Haixia; Shi, Haifeng, E-mail: haifeng.shi@gmail.com; Qi, Miao; Zhang, Lingjian; Zhang, Xingxiang; Qi, Lu

2013-07-20

Graphical abstract: SMA-g-CnOH comb-like PCMs exhibit the better thermal stability against 1-alcohols due to the protection of SMA backbones, and the degradation temperature is dependent on the side-chain length, where at 5 wt% weight loss T{sub d} increased from 193 to 257 °C with n changing from 14 to 26. SMA-g-CnOH PCMs can be widely used under 300 °C for preparation of energy-saving products and materials. - Highlights: • The length of alkyl side-chains determines the thermal energy storage ability. • SMA backbone restricts the crystallization of alkyl side groups. • SMA-g-CnOH PCMs have the better thermal stability against 1-alcohols. - Abstract: A series of comb-like copolymeric phase change materials (SMA-g-CnOH) composed of poly(styrene-co-maleic anhydride) (SMA) and 1-alcohols CnOH with n = 14, 16, 18 or 26, respectively, was synthesized through grafting reaction. The structure and thermal properties of SMA-g-CnOH were investigated by {sup 1}H nuclear magnetic resonance ({sup 1}H NMR), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and wide-angle X-ray diffraction (WAXD). The DSC analysis indicates that SMA-g-CnOH exhibit good structure stability with phase change enthalpies changing from 37.9 to 110.7 J g{sup −1}. The results showed that the low thermal efficiency of SMA-g-CnOH was ascribed to the small CH{sub 2} segments of side chains participating in the assembled structure of side-chain crystallites. Their advantageous structural stability and thermal performance of SMA-g-CnOH were favorable for phase change materials in the thermal energy storage systems. Additionally, the influence of side-chain length on thermal properties of SMA-g-CnOH also was discussed in detail in combination with the published results.

Investigation of Na-CO{sub 2} Reaction with Initial Reaction in Various Reacting Surface

Energy Technology Data Exchange (ETDEWEB)

Kim, Hyun Su; Park, Gunyeop; Kim, Soo Jae; Park, Hyun Sun; Kim, Moo Hwan [POSTECH, Pohang (Korea, Republic of); Wi, Myung-Hwan [KAERI, Daejeon (Korea, Republic of)

2015-10-15

The reaction products that cause oxidation and erosion are threaten the heat transfer tubes so that it is necessary to investigate Na-CO{sub 2} reaction according to various experimental parameter. Unlike SWR, Na-CO{sub 2} reaction is more complex to deal with reaction kinetics. Since a comprehensive understanding of Na-CO{sub 2} reaction mechanism is crucial for the safety analysis, the reaction phenomenon under the various conditions was investigated. The current issue is to make a database for developing computational code for CO{sub 2} gas leak situation because it is experimentally difficult to analyze the actual accident situation. Most studies on Na-CO{sub 2} interaction reports that chemical reaction is getting vigorous as temperature increased and reactivity is sensitive as temperature change between 400 .deg. C and 600 .deg. C. Therefore, temperature range is determined based on the operating condition (450 - 500 .deg. C) of KALIMER-600 employed as supercritical CO{sub 2} brayton cycle energy conversion system for Na-CO{sub 2} heat exchanger. And next parameter is sodium surface area which contact between sodium and CO{sub 2} when CO{sub 2} is injected into sodium pool in the accident situation. So, the fundamental surface reaction is experimentally studied in the range of 8 - 12cm{sup 2}. Additionally, it has been reported in recent years that CO{sub 2} Flow rate affects reactivity less significantly and CO{sub 2} flow rate is assumed that 5 SLPM (standard liter per minute) is suitable as a basis for a small leakage. The finally selected control parameters is sodium temperature and reacting surface area with constant CO{sub 2} flow rate. Na-CO{sub 2} reaction test is performed for investigating risk of potential accident which contacts with liquid sodium and CO{sub 2}. Amount of reaction is saturated as time passed because of kept a balance between production of solid phase reaction products and amount of diffusivity. These results contribute to make a

Characterization of polyethyleneterephthalate (PET) based proton exchange membranes prepared by UV-radiation-induced graft copolymerization of styrene

Energy Technology Data Exchange (ETDEWEB)

Ahmed, Mostak; Khan, Mohammad B.; Alam, S. Shamsul; Khan, M. Anwar H. [Department of Chemistry, Shahjalal University of Science and Technology, Sylhet 3114 (Bangladesh); Khan, Mubarak A. [Radiation and Polymer Chemistry Laboratory, Institute of Nuclear Science and Technology, Bangladesh Atomic Energy Commission, P.O. Box 3787, Dhaka (Bangladesh); Halim, Md. Abdul [Department of Chemistry, Jahangirnagar University, savar, Dhaka (Bangladesh)

2011-01-15

Polymer electrolyte membranes (PEMs) were successfully prepared by simultaneous ultraviolet (UV) radiation-induced graft copolymerization of styrene (35 vol.% concentration) onto poly(ethyleneterephthalate) (PET) film, followed by sulfonation on the styrene monomer units in the grafting chain using 0.05 M chlorosulfonic acid (ClSO{sub 3}H). The radiation grafting and the sulfonation have been confirmed by titrimetric and gravimetric analyses as well as Fourier Transform Infrared (FTIR) spectroscopy. The maximum ion-exchange capacity (IEC) of the PEM was measured to be 0.04385 mmol g{sup -1} at its highest level of grafting and sulfonation. They exhibited high thermal and mechanical properties as well as oxidative stability. They are highly stable in H{sub 2}SO{sub 4} solutions and can be used in the acidic fuel cells. The membranes showed low water uptake as well as low proton conductivity than Nafion. In this study, the preparation of PEMs from commodity-type polymers is found to be very inexpensive and is a suitable candidate for applications in fuel cells. (author)

Reaction rate of hydrolysis of iodine

International Nuclear Information System (INIS)

Miyake, Yoshikazu; Eguchi, Wataru; Adachi, Motonari

1979-01-01

Absorption rates of dilute iodine vapor contained in air by aqueous mixtures of sodium hydroxide and boric acid were measured using a laminar liquid jet column absorber at 298 K. Absorption rates in this system are controlled by a series of complex reactions taking place in the liquid phase. The reaction rate constant of iodine hydrolysis in the aqueous phase was determined from the absorption rates observed under the conditions that the base-catalytic hydrolysis reaction of iodine can be considered to be irreversible and that other reactions can be neglected. The absorption rates calculated theoretically with the rate constant value obtained above were in good accordance with the whole experimental data observed for a wide range of experimental conditions. (author)

Application of multi-step direct reaction theory to 14 MeV neutron reaction, 3 (n,. cap alpha. )

Energy Technology Data Exchange (ETDEWEB)

Kumabe, I.; Matoba, M.; Fukuda, K. [Kyushu Univ., Fukuoka (Japan). Faculty of Engineering; Ikegami, H.; Muraoka, M [eds.

1980-01-01

Multi-step direct-reaction theory proposed by Tamura et al. has been applied to continuous spectra of the 14 MeV (n, ..cap alpha..) reaction with some modifications. Calculated results reproduce well the experimental energy and angular distributions of the 14 MeV (n, ..cap alpha..) reactions.

Coupled-reaction-channel analysis of the (d,6Li) reaction on 24Mg and 26Mg to low-lying states

International Nuclear Information System (INIS)

Oelert, W.

1986-01-01

Experimental spectroscopic factors of the alpha-transfer reaction on nuclei of the sd-shell show rather strong inconsistencies and scatter much more strongly than explainable by the quoted errors. The poorer the quality of agreement between experimental and theoretical angular distribution shapes, the more inconsistent the comparison of spectroscopic factors either between different experiments or between theory and experiment. In view of the strong deformation of nuclei in the lower part of the sd-shell, higher-order reaction mechanisms are expected. A coupled-reaction-channel analysis for the transitions to the 0 + , 2 + , and 4 + states of the ground-state bands in 20 Ne and 22 Ne excited via the (d, 6 Li) reaction yields good agreement between experimental and theoretical angular distribution shapes as well as spectroscopic information. (orig.)

[Reaction mechanism studies of heavy ion induced nuclear reactions]: Annual progress report, October 1987

International Nuclear Information System (INIS)

Mignerey, A.C.

1987-10-01

The experiments which this group has been working on seek to define the reaction mechanisms responsible for complex fragment emission in heavy ion reactions. The reactions studied are La + La, La + Al, and La + Cu at 46.8 MeV/u; and Ne + Ag and Ne + Au reactions at 250 MeV/u. Another experimental program at the Oak Ridge Hollifield Heavy Ion Research Facility (HHIRF) is designed to measure the excitation energy division between reaction products in asymmetric deep inelastic reactions. A brief description is given of progress to date, the scientific goals of this experiment and the plastic phoswich detectors developed for this experiment

Homogeneous graft copolymerization of styrene onto cellulose in a sulfur dioxide-diethylamine-dimethyl sulfoxide cellulose solvent

International Nuclear Information System (INIS)

Tsuzuki, M.; Hagiwara, I.; Shiraishi, N.; Yokota, T.

1980-01-01

Graft copolymerization of styrene onto cellulose was studied in a homogeneous system [SO 2 (liquid)- diethylamine (DEA)-dimethyl sulfoxide (DMSO) medium)] by γ-ray mutual irradiation technique. At the same time, homopolymerization of styrene was also examined separately in DMSO, SO 2 -DMSO, DEA-DMSO, and SO 2 -DEA-DMSO media by the same technique. Polymerization of styrene hardly occurs on concentrations above 10 mole SO 2 -DEA complex per mole glucose unit. Maximum percent grafting was obtained in concentrations of 4 mole, after which it decreased rapidly. Total conversion and percent grafting increased with the irradiation time. The value (=0.55) of the slope of the total conversion rate plotted against the dose was only a little higher than the 1/2 which was expected from normal kinetics. No retardation in homopolymerization of styrene in DMSO, SO 2 -DMSO, and DEA-DMSO was evident, while the retardation of homopolymerization in the SO 2 -DEA-DMSO medium was measurable. Sulfur atoms were detected in the polymers obtained in both of SO 2 -DMSO and SO 2 -DEA-DMSO solutions. All of the molecular weights of polymers obtained in the present experiment were very low

Graft Copolymerization of Methyl Methacrylate Monomer onto Starch and Natural Rubber Latex Initiated by Gamma Irradiation

Directory of Open Access Journals (Sweden)

S. Iskandar

2011-04-01

Full Text Available To obtain the degradable plastic, the graft copolymerization of methyl methacrylate onto starch and natural rubber latex was conducted by a simultaneous irradiation technique. Gamma-ray from cobalt-60 source was used as the initiator. The grafted copolymer of starch-polymethyl methacrylate and the grafted copolymer of natural rubber-polymethyl methacrylate were mixed in the blender, and dried it in the oven. The dried grafted copolymer mixture was then molded using hydraulic press machine. The effect of irradiation dose, composition of the grafted copolymer mixture, film forming condition and recycle effect was evaluated. The parameters observed were tensile strength, gel fraction and soil burial degradability of grafted copolymer mixture. It was found that the tensile strength of grafted copolymer mixture increased by -ray irradiation. Increasing of the grafted copolymer of natural rubber-polymethyl methacrylate content, the gel fraction and tensile strength of the grafted copolymer mixture increased. The tensile strength of the grafted copolymer mixture was increased from 18 MPa to 23 MPa after recycled (film forming reprocessed 3 times. The grafted copolymer mixture was degraded completely after soil buried for 6 months

A dynamical theory of incomplete fusion reactions: The breakup-fusion reaction approach

International Nuclear Information System (INIS)

Udagawa, T.

1984-01-01

A dynamical theory of partial fusion reactions is presented, which may fill the gap between direct and compound nuclear reaction theories. With the new theory one can calculate partial fusion taking place in three-body (and many more) channels reached via direct reactions, e.g., breakup and knockout reactions. The authors present first the results for the cross section for such reactions, taking as an example breakup followed by fusion. They then discuss a physical picture which emerges from their theory, namely that the partial fusion reactions, particularly of the massive-transfer type, take place in a so-called deep peripheral region. It is also shown that the deep peripheral character of such processes diminishes as the mass of the fused system decreases, so that the reactions essentially evolve to the usual peripheral character. Finally, comparisons are made of results of numerical calculations with experimental data, taking as an example the /sup 159/Tb(/sup 14/N,α) reaction with E/sub lab/ = 95 MeV

An experimental and theoretical kinetic study of the reaction of OH radicals with tetrahydrofuran

KAUST Repository

Giri, Binod

2016-06-24

Tetrahydrofuran (CHO, THF) and its alkylated derivatives of the cyclic ether family are considered to be promising future biofuels. They appear as important intermediates during the low-temperature oxidation of conventional hydrocarbon fuels and of heavy biofuels such as long-chain fatty acid methyl esters. The reaction of tetrahydrofuran with OH radicals was investigated in a shock tube, over a temperature range of 800-1340 K and at pressures near 1.5 bar. Hydroxyl radicals were generated by the rapid thermal decomposition of tert-butyl hydroperoxide, and a UV laser absorption technique was used to monitor the mole fraction of OH radicals. High-level CCSD(T)/cc-pV(D,T)Z//MP2/aug-cc-pVDZ quantum chemical calculations were performed to explore the chemistry of the THF+OH reaction system. Our calculations reveal that the THF+OH (R1) reaction proceeds via either direct or indirect H-abstraction from various sites, leading to the formation of tetrahydrofuran-2-yl (THF-R2) or tetrahydrofuran-3-yl (THF-R3) radicals and water. Theoretical kinetic analysis revealed that both channels are important under conditions relevant to combustion. To our knowledge, this is the first direct experimental and theoretical kinetic study of the reaction of tetrahydrofuran with OH radicals at high temperatures. The following theoretical rate expressions (in units of cmmols) are recommended for combustion modeling in the temperature range 800-1350 K: . k1(T)=4.11×1040.16em0ex(TK)2.69exp(1316.80.16em0exKT)2.em0ex0.16em0ex(THF+OH→Products) . k2(T)=6.930.16em0ex×10110.16em0ex(TK)0.41exp(-106.80.16em0exKT)2.em0ex0.16em0ex(THF+OH→THF-R20.16em0ex+H2O) . k3(T)=4.120.16em0ex×1030.16em0ex(TK)3.02exp(456.90.16em0exKT)2.em0ex0.16em0ex(THF+OH→THF-R30.16em0ex+H2O) . .

Evaluation of excitation functions for isomeric levels in neutron reactions

International Nuclear Information System (INIS)

Grudzevich, O.T.; Zelenetskij, A.V.; Zolotarev, K.I.; Kornilov, N.V.; Pashchenko, A.B.

1993-07-01

The authors consider the use of theoretical models to describe experimental excitation functions for isomeric levels in neutron reactions and to predict the cross-sections when no experimental data are available. It is shown that, in many cases, experimental data can be described quite satisfactorily by calculations without adjustment of parameters. For threshold reactions at a neutron energy of ∼ 14 MeV the agreement between calculated and experimental isomeric ratios is ∼ 20%, and is determined mainly by errors in the experimental ratios. However, for some reactions there are considerable differences between experimental and calculated data, which are due, in the authors' opinion, to uncertainties in the schemes of the low-lying levels and of gamma transitions between levels and to the spin dependence of level density. The small isomeric ratio values R<0.1 are described with the lowest accuracy. A formula is suggested for the energy dependence of the isomeric ratio in the (n,γ) reaction. (author)

A review of reaction rates in high temperature air

Science.gov (United States)

Park, Chul

1989-01-01

The existing experimental data on the rate coefficients for the chemical reactions in nonequilibrium high temperature air are reviewed and collated, and a selected set of such values is recommended for use in hypersonic flow calculations. For the reactions of neutral species, the recommended values are chosen from the experimental data that existed mostly prior to 1970, and are slightly different from those used previously. For the reactions involving ions, the recommended rate coefficients are newly chosen from the experimental data obtained more recently. The reacting environment is assumed to lack thermal equilibrium, and the rate coefficients are expressed as a function of the controlling temperature, incorporating the recent multitemperature reaction concept.

Energy spectrum of 208Pb(n,x) reactions

Science.gov (United States)

Tel, E.; Kavun, Y.; Özdoǧan, H.; Kaplan, A.

2018-02-01

Fission and fusion reactor technologies have been investigated since 1950's on the world. For reactor technology, fission and fusion reaction investigations are play important role for improve new generation technologies. Especially, neutron reaction studies have an important place in the development of nuclear materials. So neutron effects on materials should study as theoretically and experimentally for improve reactor design. For this reason, Nuclear reaction codes are very useful tools when experimental data are unavailable. For such circumstances scientists created many nuclear reaction codes such as ALICE/ASH, CEM95, PCROSS, TALYS, GEANT, FLUKA. In this study we used ALICE/ASH, PCROSS and CEM95 codes for energy spectrum calculation of outgoing particles from Pb bombardment by neutron. While Weisskopf-Ewing model has been used for the equilibrium process in the calculations, full exciton, hybrid and geometry dependent hybrid nuclear reaction models have been used for the pre-equilibrium process. The calculated results have been discussed and compared with the experimental data taken from EXFOR.

Polymerization of an acetoxyvinyl substituted chlorocyclophosphazene

NARCIS (Netherlands)

Bosscher, G; Jekel, AP; vandeGrampel, JC

The vinyl acetate derivative, gem-isopropyl-2-(alpha-acetoxyvinyl)tetrachlorocyclotriphosphazene (1), has been used in radical homopolymerization and copolymerization reactions with methyl methacrylate, (MMA) and styrene. The 1,1-disubstituted olefin did not undergo radical homopolymerization.

Experimental study of the 22Ne(p,γ)23Na reaction and its implications for novae scenarios

International Nuclear Information System (INIS)

Menzel, Marie-Luise

2013-01-01

The 22 Ne(p,γ) 23 Na reaction belongs to the catalytic neon-sodium cycle and has an important role in the explosive hydrogen burning. The neon-sodium cycle takes place at temperatures of T = 0.1 - 0.5 GK and is assumed to occur in different astrophysical systems: e.g. in novae, in super novae of type Ia and during the shell-burning of red giant branch stars. The implications of 22 Ne(p,γ) 23 Na and the neon-sodium cycle in a nova scenario have been studied by using the nuclear network code libnucnet at GSI in Darmstadt. A nova is an outburst of matter in a binary system consisting of a white dwarf and a red giant star. It is therefore a representative phenomenon for explosive hydrogen burning. For the calculation of the nucleosynthesis during the nova outburst, the code libnucnet requires the initial mass composition of the novae partners, the temperature and density profiles of the nova explosion and the thermonuclear reaction rates of the participating reactions. In the following, the code determined the flow and the final atomic abundance in the neon-sodium cycle during the entire nova process. Additionally, the influence of the temperature profile of the novae outburst as well as the thermonuclear reaction rate of the 22 Ne(p,γ) 23 Na reaction on the final atomic abundance in the outburst has been studied. A characteristic measure for the reactions in astrophysical environments is the thermonuclear reaction rate. The reaction rate of 22 Ne(p,γ) 23 Na has still strong uncertainties in the temperature range of T = 0.03 - 0.3 GK. These uncertainties are based on insufficient upper limits of the resonance strengths as well as the possible existence of tentative states that are populated in the energy range of E lab p = 30 - 300 keV. The research presented in this thesis is dedicated to the experimental study of the 22 Ne(p,γ) 23 Na reaction for an improved determination of the thermonuclear reaction rate. Furthermore, the implications of 22 Ne(p,γ) 23 Na and

Ozone production in the reaction of T2 and O2 gas: A comparison of experimental results and model predictions

International Nuclear Information System (INIS)

Failor, R.A.; Souers, P.C.; Magnotta, F.

1992-01-01

Ozone, predicted to be an important intermediate species in T 2 oxidation, was monitored in situ by UV absorption spectroscopy for 0.01-1.0 mol % T 2 in O 2 (1 atm, 298 K). These are the first measurements of a tritium oxidation reaction intermediate. The experimental results were compared with the predictions of the author's comprehensive model of tritium oxidation. The experimentally determined temporal variation in ozone concentration is qualitatively reproduced by the model. As predicted, the measured initial rate of ozone production varied linearly with the initial T 2 concentration ([T 2 ] o ), but with a value one-third of that predicted. The steady-state ozone concentration ([O 3 ] ss ) a factor of 4 larger than predicted for a 1.0% T 2 -O 2 mixture. Addition of H 2 to the T 2 O 2 mixture, to differentiate between the radiolytic and chemical behavior of the tritium, produced a decrease in [O 3 ] ss which was larger than predicted. Changing the reaction cell surface-to-volume ratio showed indications of minor surface removal of ozone. No reasonable variation in model input parameters brought both the predicted initial ozone production rates and steady-state concentrations of ozone into agreement with the experimental results. Though qualitative agreement was achieved, further studies, with emphasis on surface effects, are necessary to explain quantitative differences and gain a greater understanding of the oxidation mechanism. 27 refs., 11 figs., 4 tabs

Experimental Investigation of the ^{19}Ne(p,γ)^{20}Na Reaction Rate and Implications for Breakout from the Hot CNO Cycle.

Science.gov (United States)

Belarge, J; Kuvin, S A; Baby, L T; Baker, J; Wiedenhöver, I; Höflich, P; Volya, A; Blackmon, J C; Deibel, C M; Gardiner, H E; Lai, J; Linhardt, L E; Macon, K T; Need, E; Rasco, B C; Quails, N; Colbert, K; Gay, D L; Keeley, N

2016-10-28

The ^{19}Ne(p,γ)^{20}Na reaction is the second step of a reaction chain which breaks out from the hot CNO cycle, following the ^{15}O(α,γ)^{19}Ne reaction at the onset of x-ray burst events. We investigate the spectrum of the lowest proton-unbound states in ^{20}Na in an effort to resolve contradictions in spin-parity assignments and extract reliable information about the thermal reaction rate. The proton-transfer reaction ^{19}Ne(d,n)^{20}Na is measured with a beam of the radioactive isotope ^{19}Ne at an energy around the Coulomb barrier and in inverse kinematics. We observe three proton resonances with the ^{19}Ne ground state, at 0.44, 0.66, and 0.82 MeV c.m. energies, which are assigned 3^{+}, 1^{+}, and (0^{+}), respectively. In addition, we identify two resonances with the first excited state in ^{19}Ne, one at 0.20 MeV and one, tentatively, at 0.54 MeV. These observations allow us for the first time to experimentally quantify the astrophysical reaction rate on an excited nuclear state. Our experiment shows an efficient path for thermal proton capture in ^{19}Ne(p,γ)^{20}Na, which proceeds through ground state and excited-state capture in almost equal parts and eliminates the possibility for this reaction to create a bottleneck in the breakout from the hot CNO cycle.

Annual report on experimental operations and maintenance of mock-up model test facility with a full-scale reaction tube for HTTR hydrogen production system in 2004 fiscal year (Contract research)

International Nuclear Information System (INIS)

Hayashi, Koji; Ohashi, Hirofumi; Morisaki, Norihiro; Kato, Michio; Aita, Hideki; Takeda, Tetsuaki; Nishihara, Tetsuo; Inaba, Yoshitomo; Takada, Shoji; Inagaki, Yoshiyuki

2006-03-01

This is annual report on the experimental test operations and maintenances of the mock-up test facility with a full-scale reaction tube for the HTTR hydrogen production system in 2004 fiscal year. The improvement work of catalyst dust filter in combustion system was performed in May 2004, and the performance was confirmed. The sixth experimental test operation was performed from June to July 2004. Periodic inspections on boiler equipment and high-pressure gas production facilities were performed from end of July to September 2004. The seventh experimental test operation was performed from October to December 2004 for chemical reaction shutdown test. From the results, a behavior of the helium-gas cooling system, consists of steam generator and radiator, during chemical reaction shutdown was confirmed. This report is summarized with the outline and the results of the test, maintenance works and inspections, and operation records in mentioned above. (author)

Synthesis, physicochemical and biological properties of ethynyl piperidol derivatives

International Nuclear Information System (INIS)

Khalikov, D.Kh.

2012-01-01

The book presents the results of studies on the reactivity of some derivatives of ethynyl-piperidol in reactions of homo-and copolymerization, the numerical values of the constants of the initiation reaction, growth and chain termination, the parameters of molecular weight, molecular weight distribution and flexibility of polymer chins, triple-radical copolymerization results of ethynyl-piperidol derivatives with hydrophilic monomers and polyfunctional cross-linked polymers and high swelling hydrogels, as well as developed by the author the radiation-chemical grafting technique termed monomers on the surface of cellulose in a continuous manner. The experimental data on ethynyl-piperidol polymers involves with various low-, medium-and high substrates from model solutions and in biological fluids are given. On the example of three iodide ion sorption, bilirubin and serum albumin showed that for the thermodynamically favorable process make a significant contribution to the free energy terms due to the hypothetical ion exchange, the change in resonates concentration and cooperative interaction. The role of hydrophobic interaction in realization of this process is reviled. The data obtained were formulated and validated a number of scientific statements in the chemistry of biomedical polymers. The results of the practical implementation of a number of developments in medical practice are demonstrated. The hydrogel homo-and sorbent, dressings, which have shown high efficacy in the treatment of diseases complicated by endogenous and bacterial endotoxemia in acute radiation and combined radiation-thermal lesions, as well as kidney and live failure. (author)

Cross-section and reaction rates for some reactions involved in explosive nucleosynthesis

International Nuclear Information System (INIS)

Cheng, C.W.

1979-03-01

Total proton-induced and alpha-induced reaction cross sections have been determined for the 24 Mg(α,n), 25 Mg(p,n), 26 Mg(p,n), 27 Al(p,n), 28 Si(α,n), 42 Ca(p,γ), 42 Ca(α,n) and 44 Ca(p,n) reactions from energies near threshold (except the exothermic (p,γ) reaction) to about 3 to 4 MeV above threshold. The product nuclei are all positron emitters with half-lives ranging from about 3 sec to about 4 hours. From the measured cross sections reaction rates have been calculated in the temperature range 1 9 9 =1, at which the discrepancy is large. Included also are analytic forms for (p,n), (α,n), and (p,γ) reactions which can be used to describe the reaction rate within the temperature range 1 9 <=6 and which agree with the experimental rates at the discrete temperatures where the reaction rates have been calculated

High energy gamma-ray production in nuclear reactions

International Nuclear Information System (INIS)

Pinston, J.A.; Nifenecker, H.; Nifenecker, H.

1989-01-01

Experimental techniques used to study high energy gamma-ray production in nuclear reactions are reviewed. High energy photon production in nucleus-nucleus collisions is discussed. Semi-classical descriptions of the nucleus-nucleus gamma reactions are introduced. Nucleon-nucleon gamma cross sections are considered, including theoretical aspects and experimental data. High energy gamma ray production in proton-nucleus reactions is explained. Theoretical explanations of photon emission in nucleus-nucleus collisions are treated. The contribution of charged pion currents to photon production is mentioned

Reaction path simulations in multicomponent materials

International Nuclear Information System (INIS)

Seifert, H.J.

1999-01-01

The CALPHAD (calculation of phase diagrams) method is used in combination with selected experimental investigations to derive reaction paths in multicomponent systems. The method is illustrated by applying computerized thermodynamic databases and suitable software to explain quantitatively the thermal degradation of precursor-derived Si-C-N ceramics and the nitridation of titanium carbide. Reaction sequences in the Si 3 N 4 -SiC-TiC x N l-x -C-N system are illustrated by graphical representation of compatibility regions and indicated reaction paths. From these results the experimentally known microstructure development of TiC reinforced Si 3 N 4 ceramics is explained and quantitative information is provided to optimize the microstructure of such materials. The concept of reaction paths for the understanding of rapid solidification processes is shown by the example of AZ type Mg casting alloys. (orig.)

Serpentinization reaction pathways: implications for modeling approach

Energy Technology Data Exchange (ETDEWEB)

Janecky, D.R.

1986-01-01

Experimental seawater-peridotite reaction pathways to form serpentinites at 300/sup 0/C, 500 bars, can be accurately modeled using the EQ3/6 codes in conjunction with thermodynamic and kinetic data from the literature and unpublished compilations. These models provide both confirmation of experimental interpretations and more detailed insight into hydrothermal reaction processes within the oceanic crust. The accuracy of these models depends on careful evaluation of the aqueous speciation model, use of mineral compositions that closely reproduce compositions in the experiments, and definition of realistic reactive components in terms of composition, thermodynamic data, and reaction rates.

Organocatalytic aza-Michael/retro-aza-Michael reaction: pronounced chirality amplification in aza-Michael reaction and racemization via retro-aza-Michael reaction.

Science.gov (United States)

Cai, Yong-Feng; Li, Li; Luo, Meng-Xian; Yang, Ke-Fang; Lai, Guo-Qiao; Jiang, Jian-Xiong; Xu, Li-Wen

2011-05-01

A detailed experimental investigation of an aza-Michael reaction of aniline and chalcone is presented. A series of Cinchona alkaloid-derived organocatalysts with different functional groups were prepared and used in the aza-Michael and retro-aza-Michael reaction. There was an interesting finding that a complete reversal of stereoselectivity when a benzoyl group was introduced to the cinchonine and cinchonidine. The chirality amplification vs. time proceeds in the quinine-derived organocatalyst containing silicon-based bulky group, QN-TBS, -catalyzed aza-Michael reaction under solvent-free conditions. In addition, we have demonstrated for the first time that racemization was occurred in suitable solvents under mild conditions due to retro-aza-Michael reaction of the Michael adduct of aniline with chalcone. These indicate the equilibrium of retro-aza-Michael reaction and aza-Michael reaction produce the happening of chirality amplification in aza-Michael reaction and racemization via retro-aza-Michael reaction under different conditions, which would be beneficial to the development of novel chiral catalysts for the aza-Michael reactions. Copyright © 2011 Wiley-Liss, Inc.

Experimental collaboration for thick concrete structures with alkali-silica reaction

Science.gov (United States)

Ezell, N. Dianne Bull; Hayes, Nolan; Lenarduzzi, Roberto; Clayton, Dwight; Ma, Z. John; Le Pape, Sihem; Le Pape, Yann

2018-04-01

Alkali-Silica Reaction (ASR) is a reaction that occurs over time in concrete between alkaline cement paste and reactive, non-crystalline silica in aggregates. An expansive gel is formed within the aggregates which results in micro-cracks in aggregates and adjacent cement paste. The reaction requires the presence of water and has been predominantly detected in groundwater-impacted portions of below grade structures, with limited impact to exterior surfaces in above grade structures. ASR can potentially affect concrete properties and performance characteristics such as compressive strength, modulus of elasticity, shear strength, and tensile strength. Since ASR degradation often takes significant amounts of time, developing ASR detection techniques is important to the sustainability and extended operation lifetimes of nuclear power plants (NPPs). The University of Tennessee, Knoxville (UTK) in collaboration with Oak Ridge National Laboratory (ORNL) designed and built an experiment representative of typical NPP structures to study ASR in thick concrete structures.

The Reaction Wheel Pendulum

CERN Document Server

Block, Daniel J; Spong, Mark W

2007-01-01

This monograph describes the Reaction Wheel Pendulum, the newest inverted-pendulum-like device for control education and research. We discuss the history and background of the reaction wheel pendulum and other similar experimental devices. We develop mathematical models of the reaction wheel pendulum in depth, including linear and nonlinear models, and models of the sensors and actuators that are used for feedback control. We treat various aspects of the control problem, from linear control of themotor, to stabilization of the pendulum about an equilibrium configuration using linear control, t

Prediction of monomer reactivity in radical copolymerizations from transition state quantum chemical descriptors

Directory of Open Access Journals (Sweden)

Zhengde Tan

2013-01-01

Full Text Available In comparison with the Q-e scheme, the Revised Patterns Scheme: the U, V Version (the U-V scheme has greatly improved both its accessibility and its accuracy in interpreting and predicting the reactivity of a monomer in free-radical copolymerizations. Quantitative structure-activity relationship (QSAR models were developed to predict the reactivity parameters u and v of the U-V scheme, by applying genetic algorithm (GA and support vector machine (SVM techniques. Quantum chemical descriptors used for QSAR models were calculated from transition state species with structures C¹H3 - C²HR³• or •C¹H2 - C²H2R³ (formed from vinyl monomers C¹H²=C²HR³ + H•, using density functional theory (DFT, at the UB3LYP level of theory with 6-31G(d basis set. The optimum support vector regression (SVR model of the reactivity parameter u based on Gaussian radial basis function (RBF kernel (C = 10, ε = 10- 5 and γ = 1.0 produced root-mean-square (rms errors for the training, validation and prediction sets being 0.220, 0.326 and 0.345, respectively. The optimal SVR model for v with the RBF kernel (C = 20, ε = 10- 4 and γ = 1.2 produced rms errors for the training set of 0.123, the validation set of 0.206 and the prediction set of 0.238. The feasibility of applying the transition state quantum chemical descriptors to develop SVM models for reactivity parameters u and v in the U-V scheme has been demonstrated.

The Reaction of Oxy Hemoglobin with Nitrite: Mechanism, Antioxidant-Modulated Effect, and Implications for Blood Substitute Evaluation

Directory of Open Access Journals (Sweden)

Denisa Hathazi

2018-02-01

Full Text Available The autocatalytic reaction between nitrite and the oxy form of globins involves free radicals. For myoglobin (Mb, an initial binding of nitrite to the iron-coordinated oxygen molecule was proposed; the resulting ferrous-peroxynitrate species was not detected, but its decay product, the high-valent ferryl form, was demonstrated in stopped-flow experiments. Reported here are the stopped flow spectra recorded upon mixing oxy Hb (native, as well as chemically-derivatized in the form of several candidates of blood substitutes with a supraphysiological concentration of nitrite. The data may be fitted to a simple kinetic model involving a transient met-aqua form, in contrast to the ferryl detected in the case of Mb in a similar reaction sequence. These data are in line with a previous observation of a transient accumulation of ferryl Hb under auto-catalytic conditions at much lower concentrations of nitrite (Grubina, R. et al. J. Biol. Chem. 2007, 282, 12916. The simple model for fitting the stopped-flow data leaves a small part of the absorbance changes unaccounted for, unless a fourth species is invoked displaying features similar to the oxy and tentatively assigned as ferrous-peroxynitrate. Density functional theory (DFT calculations support this latter assignment. The reaction allows for differentiating between the reactivities of various chemically modified hemoglobins, including candidates for blood substitutes. Polymerization of hemoglobin slows the nitrite-induced oxidation, in sharp contrast to oxidative-stress type reactions which are generally accelerated, not inhibited. Sheep hemoglobin is found to be distinctly more resistant to reaction with nitrite compared to bovine Hb, at large nitrite concentrations (stopped-flow experiments directly observing the oxy + nitrite reaction as well as under auto-catalytic conditions. Copolymerization of Hb with bovine serum albumin (BSA using glutaraldehyde leads to a distinct increase of the lag time

The nuclear reaction n + 3He -> 1H + 3H as proximity reaction

International Nuclear Information System (INIS)

Hilber, H.C.

1982-01-01

The present thesis tries to give by means of the nuclear reaction n + 3 He -> 1 H + 3 H as proximity reaction on the three-particle system 3 He + 9 Be -> 1 H + 3 H + 8 Be an experimental verification to the second term of a multiple scattering series. The study of these rescattering effects is of great interest for the present theory of the final-state interaction. At three incident energies (7.08 MeV, 8.98 MeV, and 6.37 MeV) to detector telescopes identify the exit channel of the three-particle system in list-mode coincidence experiments according to protons and tritons. Peaks on the kinematical curves occur. The detailed study of their kinematic behaviour allows to exclude the inconcurrence to the proximity reaction lying cascade decays via intermediate states in 4 He, 9 B, and 11 B. Regarding the Coulomb interaction the experimental results can be also explained in the sense of the classical kinematics by the proximity model. (orig.) [de

Heavy ion reactions at low energies

International Nuclear Information System (INIS)

Nemes, M.C.

1985-01-01

Some general features of the heavy ion reactions at low energies are presented. Some kinds of processes are studied, such as: elastic scattering, peripherical reactions, deep inelastic collisions and fusion. Both, theoretical and experimental perspectives on this field are discussed. (L.C.) [pt

Theoretical and experimental studies of N and SF2 reaction

International Nuclear Information System (INIS)

Yu Shuqin; Zhou Xiaoguo

2000-02-01

In this paper, free radical reaction of N+SF 2 induced by dc discharge in N 2 and SF 6 system was examined. Although the NS + (m/z = 46) ion signals were detected, NS + is not the spectral carrier from obtained REMPI spectra analysis. Ab initio quantum calculation shows that NSF is the main product of N + SF 2 . It is confirmed from this calculation that NS + obtained in experiment was produced by multiphoton ionization and dissociation of NSF which is real product of N + SF 2 reaction. (author)

Activation barriers for series of exothermic homologous reactions. V. Boron group diatomic species reactions

Science.gov (United States)

Blue, Alan S.; Belyung, David P.; Fontijn, Arthur

1997-09-01

Semiempirical configuration interaction (SECI) theory is used to predict activation barriers E, as defined by k(T)=ATn exp(-E/RT). Previously SECI has been applied to homologous series of oxidation reactions of s1, s2, and s2p1 metal atoms. Here it is extended to oxidation reactions of diatomic molecules containing one s2p1 atom. E values are calculated for the reactions of BH, BF, BCl, AlF, AlCl, AlBr, GaF, GaI, InCl, InBr, InI, TlF, TlCl, TlBr, and TlI with O2, CO2, SO2, or N2O. These values correlate with the sums of the ionization potentials and Σ-Π promotion energies of the former minus the electron affinities of the latter. In the earlier work n was chosen somewhat arbitrarily, which affected the absolute values of E. Here it is shown that examination of available experimental and theoretical results allows determination of the best values of n. Using this approach yields n=1.9 for the present series. For the seven reactions which have been studied experimentally, the average deviation of the SECI activation barrier prediction from experiment is 4.0 kJ mol-1. Energy barriers are calculated for another 52 reactions.

Homopolymerization of Ethylene, 1-Hexene, Styrene and Copolymerization of Styrene With 1,3-Cyclohexadiene Using (h5-Tetramethylcyclopentadienyldimethylsilyl(N-Ar’amido-TiCl2/MAO (Ar’=6-(2-(Diethylborylphenylpyrid-2-yl, Biphen-3-yl

Directory of Open Access Journals (Sweden)

Michael R. Buchmeiser

2011-01-01

Full Text Available The propensity of a half-sandwich (η5-tetramethylcyclopentadienyl dimethylsilylamido TiIV-based catalyst bearing an auxiliary diethylboryl-protected pyridyl moiety (Ti-8, activated by methylaluminoxane (MAO to homopolymerize α-olefins such as ethylene, 1-hexene and styrene as well as to copolymerize styrene with 1,3-cyclo-hexadiene is described. The reactivity of Ti-8 was investigated in comparison to a 6-(2-(diethylborylphenylpyrid-2-yl-free analogue (Ti-3.

A study on sodium-concrete reaction

Energy Technology Data Exchange (ETDEWEB)

Pae, Jae Huem; Min, Byung Hoon; Lee, Joon Sik; Lee, Choong Hui; Chung, Ki Hong; Keum, Choong Ki [Suwon University, Suwon (Korea, Republic of)

1994-07-15

Sodium is commonly used as a coolant in liquid metal reactor. A large amount of its leakage may be possible in hypothetical accidents, even though the possibility is very low. In case that the leaked hot sodium comes in direct contact with structural concrete of liquid metal reactor, the reactor`s integrity can be challenged by the rupture of structure materials, hydrogen generation and its explosion, and release of radioactive aerosols due to sodium-concrete reaction. The knowledge of sodium-concrete reaction is evaluated to be one of the important and indispensable technologies for the establishment of safety measure in liquid metal reactor. In this study, the experimental facility of sodium-concrete reaction is to be designed, constructed and operated. And the reaction phenomena of sodium-concrete reaction is also to be analyzed through the experimental results. The aim of this study is to establish the measure of safety and protection for sodium-related facilities and to secure one of the fundamental technologies of liquid metal reactor safety. 47 refs., 7 figs., 13 tab.

Characterization of polymer-based monolithic capillary columns by inverse size-exclusion chromatography and mercury-intrusion porosimetry

NARCIS (Netherlands)

Urban, J.; Eeltink, S.; Jandera, P.; Schoenmakers, P.J.

2008-01-01

Organic-polymer monolithic capillary columns were prepared in fused-silica capillaries by a radical copolymerization reaction of butyl methacrylate and ethylene dimethacrylate monomers in the presence of 1,4-butanediol and 1-propanol as porogen solvents and azobisisobutyronitrile as the initiator.

Substituted 2,1,3-Benzothiadiazole- And Thiophene-Based Polymers for Solar Cells - Introducing a New Thermocleavable Precursor

DEFF Research Database (Denmark)

Petersen, Martin Helgesen; Gevorgyan, Suren; Krebs, Frederik C

2009-01-01

Alkoxysubstituted and unsubstituted 2,1,3-benzothiadiazoles were prepared and copolymerized with substituted and unsubstituted thiophenes using both Stille and Yamamoto cross-coupling reactions. One class of the materials bore thermally labile ester groups. The materials were all found to have...

Extension of the energy range of the experimental activation cross-sections data of longer-lived products of proton induced nuclear reactions on dysprosium up to 65MeV.

Science.gov (United States)

Tárkányi, F; Ditrói, F; Takács, S; Hermanne, A; Ignatyuk, A V

2015-04-01

Activation cross-sections data of longer-lived products of proton induced nuclear reactions on dysprosium were extended up to 65MeV by using stacked foil irradiation and gamma spectrometry experimental methods. Experimental cross-sections data for the formation of the radionuclides (159)Dy, (157)Dy, (155)Dy, (161)Tb, (160)Tb, (156)Tb, (155)Tb, (154m2)Tb, (154m1)Tb, (154g)Tb, (153)Tb, (152)Tb and (151)Tb are reported in the 36-65MeV energy range, and compared with an old dataset from 1964. The experimental data were also compared with the results of cross section calculations of the ALICE and EMPIRE nuclear model codes and of the TALYS nuclear reaction model code as listed in the latest on-line libraries TENDL 2013. Copyright © 2015. Published by Elsevier Ltd.

Comparison of calculated and experimental isotope edited FTIR difference spectra for purple bacterial photosynthetic reaction centers with different quinones incorporated into the QA binding site.

Directory of Open Access Journals (Sweden)

Nan eZhao

2013-08-01

Full Text Available Previously we have shown that ONIOM type (QM/MM calculations can be used to simulate isotope edited FTIR difference spectra for neutral ubiquinone in the QA binding site in Rhodobacter sphaeroides photosynthetic reaction centers. Here we considerably extend upon this previous work by calculating isotope edited FTIR difference spectra for reaction centers with a variety of unlabeled and 18O labeled foreign quinones incorporated into the QA binding site. Isotope edited spectra were calculated for reaction centers with 2,3-dimethoxy-5,6-dimethyl-1,4-benzoquinone (MQ0, 2,3,5,6-tetramethyl-1,4-benzoquinone (duroquinone, DQ, and 2,3-dimethyl-l,4-naphthoquinone (DMNQ incorporated, and compared to corresponding experimental spectra. The calculated and experimental spectra agree well, further demonstrating the utility and applicability of our ONIOM approach for calculating the vibrational properties of pigments in protein binding sites.The normal modes that contribute to the bands in the calculated spectra, their composition, frequency and intensity, and how these quantities are modified upon 18O labeling, are presented. This computed information leads to a new and more detailed understanding/interpretation of the experimental FTIR difference spectra. Hydrogen bonding to the carbonyl groups of the incorporated quinones is shown to be relatively weak. It is also shown that there is some asymmetry in hydrogen bonding, accounting for 10-13 cm-1 separation in the frequencies of the carbonyl vibrational modes of the incorporated quinones. The extent of asymmetry H-bonding could only be established by considering the spectra for various types of quinones incorporated into the QA binding site. The quinones listed above are tail-less. Spectra were also calculated for reaction centers with corresponding tail containing quinones incorporated, and it is found that replacement of the quinone methyl group by a phytyl or prenyl chain does not alter ONIOM calculated s

The dynamics of the Hg + Br2 reaction: elucidation of the reaction mechanism for the Br exchange reaction.

Science.gov (United States)

Jambrina, P G; Menéndez, M; Aoiz, F J

2017-06-28

In spite of its importance in the Hg atmospheric chemistry, the dynamics of the Hg + Br 2 → HgBr + Br reaction is poorly understood. In this article, we have carried out a comprehensive study of the reaction mechanism of this reaction by means of quasiclassical trajectories (QCTs) on an existing ab initio potential energy surface (PES). The reaction has a non trivial dynamics, as a consequence of its large endothermicity, the presence of a deep potential well, and the competition between the Br exchange and the collision induced dissociation processes. Our calculations demonstrate that insertion is only relevant at energies just above the reaction threshold and that, at energies above 2.3 eV, HgBr formation typically takes place via a sort of frustrated dissociation. In order to compare directly with the results obtained in extensive cross molecular beam experiments for the homologous reaction with I 2 , angular distributions in the laboratory frame for Hg + Br 2 have been simulated under similar experimental conditions. The lack of agreement at the highest energies considered suggests that either the two reactions have substantially different mechanisms or that calculations on a single PES cannot account for the dynamics at those energies.

Single proton transfer reactions on odd-even nuclei

International Nuclear Information System (INIS)

Blasi, N.

1984-01-01

This thesis is devoted to the study of one proton transfer reactions, performed with the use of the magnetic spectrograph QMG/2 of the KVI, in two regions of the mass table. Stripping and pickup reactions on the odd-A target nuclei 193 Ir and 197 Au are described in the first part. The experimental spectroscopic factors obtained are used to test several collective models that are based on coupling between bosons (phonons) and fermions. In the second part, the proton stripping reactions on 113 In and 115 In are studied. Shell model calculations are performed and applied to the experimental results. (Auth.)

Experimental investigation on material migration phenomena in micro-EDM of reaction-bonded silicon carbide

Energy Technology Data Exchange (ETDEWEB)

Liew, Pay Jun [Department of Mechanical Systems and Design, Tohoku University, Aramaki Aoba 6-6-01, Aoba-ku, Sendai, 980-8579 (Japan); Manufacturing Process Department, Faculty of Manufacturing Engineering, Universiti Teknikal Malaysia Melaka, Hang Tuah Jaya, 76100, Durian Tunggal, Melaka (Malaysia); Yan, Jiwang, E-mail: yan@mech.keio.ac.jp [Department of Mechanical Engineering, Faculty of Science and Technology, Keio University, Hiyoshi 3-14-1, Kohoku-ku, Yokohama, 223-8522 (Japan); Kuriyagawa, Tsunemoto [Department of Mechanical Systems and Design, Tohoku University, Aramaki Aoba 6-6-01, Aoba-ku, Sendai, 980-8579 (Japan)

2013-07-01

Material migration between tool electrode and workpiece material in micro electrical discharge machining of reaction-bonded silicon carbide was experimentally investigated. The microstructural changes of workpiece and tungsten tool electrode were examined using scanning electron microscopy, cross sectional transmission electron microscopy and energy dispersive X-ray under various voltage, capacitance and carbon nanofibre concentration in the dielectric fluid. Results show that tungsten is deposited intensively inside the discharge-induced craters on the RB-SiC surface as amorphous structure forming micro particles, and on flat surface region as a thin interdiffusion layer of poly-crystalline structure. Deposition of carbon element on tool electrode was detected, indicating possible material migration to the tool electrode from workpiece material, carbon nanofibres and dielectric oil. Material deposition rate was found to be strongly affected by workpiece surface roughness, voltage and capacitance of the electrical discharge circuit. Carbon nanofibre addition in the dielectric at a suitable concentration significantly reduced the material deposition rate.

Experimental investigation on material migration phenomena in micro-EDM of reaction-bonded silicon carbide

International Nuclear Information System (INIS)

Liew, Pay Jun; Yan, Jiwang; Kuriyagawa, Tsunemoto

2013-01-01

Material migration between tool electrode and workpiece material in micro electrical discharge machining of reaction-bonded silicon carbide was experimentally investigated. The microstructural changes of workpiece and tungsten tool electrode were examined using scanning electron microscopy, cross sectional transmission electron microscopy and energy dispersive X-ray under various voltage, capacitance and carbon nanofibre concentration in the dielectric fluid. Results show that tungsten is deposited intensively inside the discharge-induced craters on the RB-SiC surface as amorphous structure forming micro particles, and on flat surface region as a thin interdiffusion layer of poly-crystalline structure. Deposition of carbon element on tool electrode was detected, indicating possible material migration to the tool electrode from workpiece material, carbon nanofibres and dielectric oil. Material deposition rate was found to be strongly affected by workpiece surface roughness, voltage and capacitance of the electrical discharge circuit. Carbon nanofibre addition in the dielectric at a suitable concentration significantly reduced the material deposition rate.

Heavy ion transfer reactions

International Nuclear Information System (INIS)

Weisser, D.C.

1977-06-01

To complement discussions on the role of γ rays in heavy ion induced reactions, the author discusses the role played by particle detection. Transfer reactions are part of this subject and are among those in which one infers the properties of the residual nucleus in a reaction by observing the emerging light nucleus. Inelastic scattering ought not be excluded from this subject, although no particles are transferred, because of the role it plays in multistep reactions and in fixing O.M. parameters describing the entrance channel of the reaction. Heavy ion transfer reaction studies have been under study for some years and yet this research is still in its infancy. The experimental techniques are difficult and the demands on theory rigorous. One of the main products of heavy ion research has been the thrust to re-examine the assumptions of reaction theory and now include many effects neglected for light ion analysis. This research has spurred the addition of multistep processes to simple direct processes and coupled channel calculations. (J.R.)

RADIOCHEMICAL YIELDS OF GRAFT POLYMERIZATION REACTIONS OF CELLULOSE

Energy Technology Data Exchange (ETDEWEB)

Arthur, Jr, J C; Blouin, F A

1963-12-15

The preparation of radioinduced graft polymers of cotton cellulose, while retaining the fibrous nature and high molecular weight of the cellulose, depended primarily on the radiochemical yields of cellulose reactions and of graft polymerization reactions. Yields of the initial major molecular changes in cellulosic polymer indicated that, in the case of scission of the molecule and carboxyl group formation, chain reactions were not initiated by radiation; however, in the case of carbonyl group formation chain reactions were initiated but quickly terminated. Generally, experimental procedures, used in graft polymerization reactions, were: simultaneous irradiation reactions, that is, application of monomers or solutions of monomers to cellulose or chemically modified celluloses, then irradiation; and post-irradiation reactions, that is, irradiation of cellulose or chemically modified celluloses, then after removal from the field of radiation, contacting the irradiated cellulose with monomer. Some of the most important factors influencing the radiochemical yields of graft polymerization reactions, of styrene and acrylonitrile onto cellulose were: concentration of monomer in treating solution; solvent; ratio of monomer solution to cellulose; prior chemical modification of cellulose; and absence of oxygen, particularly in post-irradiation reactions. Experimental data are presented, and the direct and indirect effects of Co/sup 60/ gamma radiation on these reactions are discussed. (auth)

Laboratory approaches of nuclear reactions involved in primordial and stellar nucleosynthesis

International Nuclear Information System (INIS)

Rolfs, C.; California Inst. of Tech., Pasadena

1986-01-01

Laboratory-based studies of primordial and stellar nucleosynthesis are reviewed, with emphasis on the nuclear reactions induced by charged particles. The analytical approach used to investigate nuclear reactions associated with stellar reactions is described, as well as the experimental details and procedures used to investigate nuclear reactions induced by charged particles. The present knowledge of some of the key reactions involved in primordial nucleosynthesis is discussed, along with the progress and problems of nuclear reactions involved in the hydrogen and helium burning phases of a star. Finally, a description is given of new experimental techniques which might be useful for future experiments in the field of nuclear astrophysics. (U.K.)

Accurate and approximate thermal rate constants for polyatomic chemical reactions

International Nuclear Information System (INIS)

Nyman, Gunnar

2007-01-01

In favourable cases it is possible to calculate thermal rate constants for polyatomic reactions to high accuracy from first principles. Here, we discuss the use of flux correlation functions combined with the multi-configurational time-dependent Hartree (MCTDH) approach to efficiently calculate cumulative reaction probabilities and thermal rate constants for polyatomic chemical reactions. Three isotopic variants of the H 2 + CH 3 → CH 4 + H reaction are used to illustrate the theory. There is good agreement with experimental results although the experimental rates generally are larger than the calculated ones, which are believed to be at least as accurate as the experimental rates. Approximations allowing evaluation of the thermal rate constant above 400 K are treated. It is also noted that for the treated reactions, transition state theory (TST) gives accurate rate constants above 500 K. TST theory also gives accurate results for kinetic isotope effects in cases where the mass of the transfered atom is unchanged. Due to neglect of tunnelling, TST however fails below 400 K if the mass of the transferred atom changes between the isotopic reactions

Experimental measurements of the 15O(alpha,gamma)19Ne reaction rate and the stability of thermonuclear burning on accreting neutron stars

International Nuclear Information System (INIS)

Fisker, J; Tan, W; Goerres, J; Wiescher, M; Cooper, R

2007-01-01

Neutron stars in close binary star systems often accrete matter from their companion stars. Thermonuclear ignition of the accreted material in the atmosphere of the neutron star leads to a thermonuclear explosion which is observed as an X-ray burst occurring periodically between hours and days depending on the accretion rate. The ignition conditions are characterized by a sensitive interplay between the accretion rate of the fuel supply and its depletion rate by nuclear burning in the hot CNO cycle and the rp-process. For accretion rates close to stable burning the burst ignition therefore depends critically on the hot CNO breakout reaction 15 O(α, γ) 19 Ne that regulates the flow between the hot CNO cycle and the rapid proton capture process. Until recently, the 15 O(α, γ) 19 Ne reaction rate was not known experimentally and the theoretical estimates carried significant uncertainties. In this paper we perform a parameter study of the uncertainty of this reaction rate and determine the astrophysical consequences of the first measurement of this reaction rate. Our results corroborate earlier predictions and show that theoretically burning remains unstable up to accretion rates near the Eddington limit, in contrast to astronomical observations

The study on grafting comonomer of n-butyl acrylate and styrene onto poly(ethylene terephthalate) film by gamma-ray induced graft copolymerization

Energy Technology Data Exchange (ETDEWEB)

Ping Xiang; Wang Mozhen [CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, Anhui 230026 (China); Ge Xuewu, E-mail: xwge@ustc.edu.c [CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, Anhui 230026 (China)

2010-09-15

Poly(ethylene terephthalate) (PET) film was successfully grafted with n-butyl acrylate and styrene comonomer through gamma-ray induced graft copolymerization. The degree of grafting (DG) and the composition of grafted side chain were characterized by {sup 1}H NMR. It was found that St can inhibit the homopolymerization of BA effectively and increase the DG when the concentration of comonomer mixture is kept constant. The proportion of St to BA in grafted side chain has a positive dependence on the feed ratio of St, which ultimately approaches the feed ratio. The thermal properties of poly(ethylene terephthalate)-graft-poly(n-butyl acrylate-co-styrene) (PET-g-P(BA-co-St)) films were investigated by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). The T{sub g} of PET decreases with the DG, indicating that the grafted P(BA-co-St) copolymer has good compatibility with PET backbone.

Spallation reactions; Reactions de spallation

Energy Technology Data Exchange (ETDEWEB)

Cugon, J.

1996-12-31

Spallation reactions dominate the interactions of hadrons with nuclei in the GeV range (from {approx} 0.1 to {approx} 10 GeV). They correspond to a sometimes important ejection of light particles leaving most of the time a residue of mass commensurate with the target mass. The main features of the experimental data are briefly reviewed. The most successful theoretical model, namely the intranuclear cascade + evaporation model, is presented. Its physical content, results and possible improvements are critically discussed. Alternative approaches are shortly reviewed. (author). 84 refs.

Surface-Activated Coupling Reactions Confined on a Surface.

Science.gov (United States)

Dong, Lei; Liu, Pei Nian; Lin, Nian

2015-10-20

Chemical reactions may take place in a pure phase of gas or liquid or at the interface of two phases (gas-solid or liquid-solid). Recently, the emerging field of "surface-confined coupling reactions" has attracted intensive attention. In this process, reactants, intermediates, and products of a coupling reaction are adsorbed on a solid-vacuum or a solid-liquid interface. The solid surface restricts all reaction steps on the interface, in other words, the reaction takes place within a lower-dimensional, for example, two-dimensional, space. Surface atoms that are fixed in the surface and adatoms that move on the surface often activate the surface-confined coupling reactions. The synergy of surface morphology and activity allow some reactions that are inefficient or prohibited in the gas or liquid phase to proceed efficiently when the reactions are confined on a surface. Over the past decade, dozens of well-known "textbook" coupling reactions have been shown to proceed as surface-confined coupling reactions. In most cases, the surface-confined coupling reactions were discovered by trial and error, and the reaction pathways are largely unknown. It is thus highly desirable to unravel the mechanisms, mechanisms of surface activation in particular, of the surface-confined coupling reactions. Because the reactions take place on surfaces, advanced surface science techniques can be applied to study the surface-confined coupling reactions. Among them, scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) are the two most extensively used experimental tools. The former resolves submolecular structures of individual reactants, intermediates, and products in real space, while the latter monitors the chemical states during the reactions in real time. Combination of the two methods provides unprecedented spatial and temporal information on the reaction pathways. The experimental findings are complemented by theoretical modeling. In particular, density

The effects of acute bout of cycling on auditory & visual reaction times.

Science.gov (United States)

Ashnagar, Zinat; Shadmehr, Azadeh; Jalaei, Shohreh

2015-04-01

The purpose of this study was to investigate the effects of an acute bout of cycling exercise on auditory choice reaction time, visual choice reaction time, auditory complex choice reaction time and visual complex choice reaction time. 29 subjects were randomly divided into experimental and control groups. The subjects of the experimental group carried out a single bout of submaximal cycling exercise. The auditory choice reaction time, visual choice reaction time, auditory complex choice reaction time and visual complex choice reaction times were measured before and after the exercise session. The reaction time tests were taken from the subjects by using Speed Anticipation and Reaction Tester (SART) software. In the control group, the reaction time tests were performed by the subjects with an interval of 30 min. In the experimental group, the percentage changes of mean auditory choice and complex choice reaction time values were significantly decreased in comparison with the control group (P visual choice and complex choice reaction times were decreased after the exercise, the changes were not significant (P > 0.05). An acute bout of cycling exercise improved the speed of auditory and visual reaction times in healthy young females. However, these positive changes were significantly observed only in the auditory reaction time tests in comparison with the control group. Copyright © 2014 Elsevier Ltd. All rights reserved.

Quantitative determination of insulin entrapment efficiency in triblock copolymeric nanoparticles by high-performance liquid chromatography.

Science.gov (United States)

Xu, Xiongliang; Fu, Yao; Hu, Haiyan; Duan, Yourong; Zhang, Zhirong

2006-04-11

A rapid and effective isocratic chromatographic procedure was described in this paper for the determination of insulin entrapment efficiency (EE) in triblock copolymeric nanoparticles using reversed-phase high-performance liquid chromatography (RP-HPLC) with an ultraviolet/visible detector at low flow rate. The method has been developed on a Shimadzu Shim-pack VP-ODS column (150 mm x 4.6 mm, 5 microm, Chiyoda-Ku, Tokyo, Japan) using a mixture of 0.2 M sodium sulfate anhydrous solution adjusted to pH 2.3 with phosphoric acid and acetonitrile (73:27, v/v) as mobile phase at the flow rate of 0.8 ml min(-1) and a 214 nm detection. The method was validated in terms of selectivity, linearity, precision, accuracy, solution stability, limit of detection (LOD) and limit of quantification (LOQ). The calibration curve was linear in the concentration range of 2.0-500.0 microg ml(-1), and the limits of detection and quantitation were 8 and 20 ng, respectively. The mean recovery of insulin from spiked samples, in a concentration range of 8-100 microg ml(-1), was 98.96% (R.S.D.= 2.51%, n = 9). The intra- and inter-assay coefficients of variation were less than 2.24%. The proposed method has the advantages of simple pretreatment, rapid isolation, high specificity and precision, which can be used for direct analysis of insulin in commercially available raw materials, formulations of nanoparticles, and drug release as well as stability studies.

Reaction network modelling for kinetic parameters of pyrolytic reactions of CHON extractants in nuclear fuel processing waste management. Contributed Paper IT-07

International Nuclear Information System (INIS)

Gaikar, Vilas G.; Thaore, Vaishali

2014-01-01

The recovery and purification of plutonium (Pu) from uranium (U) and of U from Thorium (Th) in spent nuclear fuel reprocessing is accomplished by processes that employ organophosphorous compounds as extractants.The main objective of the present work was to develop a suitable kinetic model and to determine the kinetic parameters of the set of reactions involved in the pyrolysis of amides by fitting the experimental data in the reaction network model. The experimental data and analysis are expected to be useful in the steam pyrolysis of amide waste in fuel reprocessing in the nuclear industry. The basic approach was to understand the reaction mechanism of the steam pyrolysis of amides and then to estimate the reaction rate constants for the generation and consumption of different species by solving the model equations, allowing for the determination of important species in the reaction network

Experimental study of the {sup 22}Ne(p,{gamma}){sup 23}Na reaction and its implications for novae scenarios

Energy Technology Data Exchange (ETDEWEB)

Menzel, Marie-Luise

2013-08-01

The {sup 22}Ne(p,{gamma}){sup 23}Na reaction belongs to the catalytic neon-sodium cycle and has an important role in the explosive hydrogen burning. The neon-sodium cycle takes place at temperatures of T = 0.1 - 0.5 GK and is assumed to occur in different astrophysical systems: e.g. in novae, in super novae of type Ia and during the shell-burning of red giant branch stars. The implications of {sup 22}Ne(p,{gamma}){sup 23}Na and the neon-sodium cycle in a nova scenario have been studied by using the nuclear network code libnucnet at GSI in Darmstadt. A nova is an outburst of matter in a binary system consisting of a white dwarf and a red giant star. It is therefore a representative phenomenon for explosive hydrogen burning. For the calculation of the nucleosynthesis during the nova outburst, the code libnucnet requires the initial mass composition of the novae partners, the temperature and density profiles of the nova explosion and the thermonuclear reaction rates of the participating reactions. In the following, the code determined the flow and the final atomic abundance in the neon-sodium cycle during the entire nova process. Additionally, the influence of the temperature profile of the novae outburst as well as the thermonuclear reaction rate of the {sup 22}Ne(p,{gamma}){sup 23}Na reaction on the final atomic abundance in the outburst has been studied. A characteristic measure for the reactions in astrophysical environments is the thermonuclear reaction rate. The reaction rate of {sup 22}Ne(p,{gamma}){sup 23}Na has still strong uncertainties in the temperature range of T = 0.03 - 0.3 GK. These uncertainties are based on insufficient upper limits of the resonance strengths as well as the possible existence of tentative states that are populated in the energy range of E{sup lab}{sub p} = 30 - 300 keV. The research presented in this thesis is dedicated to the experimental study of the {sup 22}Ne(p,{gamma}){sup 23}Na reaction for an improved determination of the

Experimental cross section evaluation for innovative 99Mo production via the (α,n) reaction on 96Zr target

International Nuclear Information System (INIS)

Pupillo, Gaia; Gambaccini, M.; Esposito, J.; Haddad, F.; Michel, N.

2014-01-01

The recent crisis of 99 Mo production by nuclear reactors caused an unexpected worldwide 99m Tc shortening, forcing the international scientific community to find alternative production routes for these vital nuclides. One of the possibilities is to replace the current reactor-based method with the accelerator-based one. The aim of this work is the experimental evaluation of the 96 Zr(α,n) 99 Mo reaction, using the well known stacked foil technique with natural Zr targets, in the energy range 33-8 MeV. The results were compared with the published experimental values, finding good agreement in the trend of the cross section but at higher peak value. The results refer to 100% enriched 96 Zr target. The cross section values measured in the different irradiations show excellent agreement and indicate that the ideal energy range for 99 Mo production is 13-25 MeV. In comparison with the literature, there is good agreement in the trend of the cross section but at higher peak value. The 96 Zr(α,n) 99 Mo reaction is an interesting alternative production route of 99 Mo aimed at the realization of 99 Mo/ 99 mTc generators. Using enriched 96 Zr as target, 99 Mo is the only radioactive Mo-isotope produced, while using natural Zr as target, the resulting 99 Mo still has an high radioisotopic purity (only the radioactive 93 Mo is co-produced), but a lower specific activity. In both cases no Tc-nuclides are directly produced in target and the high purity 99m Tc results only from the decay of 99 Mo

Correlations between reaction product yields as a tool for probing heavy-ion reaction scenarios

International Nuclear Information System (INIS)

Gawlikowicz, W.; Agnihotri, D. K.; Baldwin, S. A.; Schroeder, W. U.; Toke, J.; Charity, R. J.; Sarantites, D. G.; Sobotka, L. G.; Souza, R. T. de; Barczyk, T.; Grotowski, K.; Micek, S.; Planeta, R.; Sosin, Z.

2010-01-01

Experimental multidimensional joint distributions of neutrons and charged reaction products were analyzed for 136 Xe + 209 Bi reactions at E/A=28, 40, and 62 MeV and were found to exhibit several different types of prominent correlation patterns. Some of these correlations have a simple explanation in terms of the system excitation energy and pose little challenge to most statistical decay theories. However, several other types of correlation patterns are difficult to reconcile with some, but not other, possible reaction scenarios. In this respect, correlations between the average atomic numbers of intermediate-mass fragments, on the one hand, and light particle multiplicities, on the other, are notable. This kind of multiparticle correlation provides a useful tool for probing reaction scenarios, which is different from the traditional approach of interpreting inclusive yields of individual reaction products.

Generation of Hydrogen and Methane during Experimental Low-Temperature Reaction of Ultramafic Rocks with Water

Science.gov (United States)

McCollom, Thomas M.; Donaldson, Christopher

2016-06-01

Serpentinization of ultramafic rocks is widely recognized as a source of molecular hydrogen (H2) and methane (CH4) to support microbial activity, but the extent and rates of formation of these compounds in low-temperature, near-surface environments are poorly understood. Laboratory experiments were conducted to examine the production of H2 and CH4 during low-temperature reaction of water with ultramafic rocks and minerals. Experiments were performed by heating olivine or harzburgite with aqueous solutions at 90°C for up to 213 days in glass bottles sealed with butyl rubber stoppers. Although H2 and CH4 increased steadily throughout the experiments, the levels were very similar to those found in mineral-free controls, indicating that the rubber stoppers were the predominant source of these compounds. Levels of H2 above background were observed only during the first few days of reaction of harzburgite when CO2 was added to the headspace, with no detectable production of H2 or CH4 above background during further heating of the harzburgite or in experiments with other mineral reactants. Consequently, our results indicate that production of H2 and CH4 during low-temperature alteration of ultramafic rocks may be much more limited than some recent experimental studies have suggested. We also found no evidence to support a recent report suggesting that spinels in ultramafic rocks may stimulate H2 production. While secondary silicates were observed to precipitate during the experiments, formation of these deposits was dominated by Si released by dissolution of the glass bottles, and reaction of the primary silicate minerals appeared to be very limited. While use of glass bottles and rubber stoppers has become commonplace in experiments intended to study processes that occur during serpentinization of ultramafic rocks at low temperatures, the high levels of H2, CH4, and SiO2 released during heating indicate that these reactor materials are unsuitable for this purpose.

High energy photons production in nuclear reactions

International Nuclear Information System (INIS)

Nifenecker, H.; Pinston, J.A.

1990-01-01

Hard photon production, in nucleus-nucleus collisions, were studied at beam energies between 10 and 125 MeV. The main characteristics of the photon emission are deduced. They suggest that the neutron-proton collisions in the early stage of the reaction are the main source of high energy gamma-rays. An overview of the theoretical approaches is given and compared with experimental results. Theoretical attempts to include the contribution of charged pion exchange currents to photon production, in calculations of proton-nucleus-gamma and nucleus-nucleus-gamma reactions, showed suitable fitting with experimental data

Reaction of Aldehydes/Ketones with Electron-Deficient 1,3,5-Triazines Leading to Functionalized Pyrimidines as Diels-Alder/Retro-Diels-Alder Reaction Products: Reaction Development and Mechanistic Studies.

Science.gov (United States)

Yang, Kai; Dang, Qun; Cai, Pei-Jun; Gao, Yang; Yu, Zhi-Xiang; Bai, Xu

2017-03-03

Catalytic inverse electron demand Diels-Alder (IEDDA) reactions of heterocyclic aza-dienes are rarely reported since highly reactive and electron-rich dienophiles are often found not compatible with strong acids such as Lewis acids. Herein, we disclose that TFA-catalyzed reactions of electron-deficient 1,3,5-triazines and electron-deficient aldehydes/ketones can take place. These reactions led to highly functionalized pyrimidines as products in fair to good yields. The reaction mechanism was carefully studied by the combination of experimental and computational studies. The reactions involve a cascade of stepwise inverse electron demand hetero-Diels-Alder (ihDA) reactions, followed by retro-Diels-Alder (rDA) reactions and elimination of water. An acid was required for both ihDA and rDA reactions. This mechanism was further verified by comparing the relative reactivity of aldehydes/ketones and their corresponding vinyl ethers in the current reaction system.

Electrophoretic analysis of proteinases in sodium dodecyl sulfate-polyacrylamide gels containing copolymerized radiolabeled protein substrates: Application to proenkephalin processing enzymes

Energy Technology Data Exchange (ETDEWEB)

Irvine, J.W.; Roberts, S.F.; Lindberg, I. (Louisiana State Univ. Medical Center, New Orleans (USA))

1990-10-01

A novel method is described for the zymographic analysis of proteinases in sodium dodecyl sulfate-polyacrylamide gels containing copolymerized radiolabeled protein substrates such as ({sup 35}S)methionine-labeled proenkephalin or {sup 125}I-labeled proinsulin. After electrophoresis the enzyme is reactivated and cleaves the radiolabeled in situ substrate into smaller peptides. These small peptides are able to diffuse out of the gel, leaving clear areas against a dark background when visualized by autoradiography. The technique can be used to detect as little as 200 fg of trypsin using only 50 ng (1.25 microCi) of ({sup 35}S)proenkephalin. Soluble- and membrane-bound adrenal trypsin-like enzyme were isolated from bovine adrenal chromaffin granules. Both proteinases cleaved ({sup 35}S)methionine-labeled proenkephalin but not {sup 125}I-labeled proinsulin. Moreover, both had a Mr of approximately 30,000. The potential of this technique for general use is discussed. An additional method using the synthetic fluorogenic substrate t-butoxycarbonyl Glu-Lys-Lys aminomethylcoumarin is also described.

Olefin copolymerization using atom transfer radical polymerization (ATRP)

NARCIS (Netherlands)

Venkatesh, R.; Klumperman, B.

2003-01-01

Olefin copolymers of alpha-olefins with polar monomers with various architectures remain an ultimate goal in polyolefin engineering. The present paper is a more detailed study on the copolymn. of alpha-olefins (1-octene) with acrylates (Me acrylate). Comparison of reaction kinetics between free

A view on reactions of complete fusion

International Nuclear Information System (INIS)

Delchev, I.I.; Petkov, I.J.

1978-11-01

Complete fusion reactions are analysed within the framework of a theoretical model. Energy density interaction potentials are made use of and are renormalized for the purpose. A large number of heavy ion reactions are studied and the calculated critical angular moments are compared with experimental data

Extraction of americium (III) by thermosensitive polymer gel copolymerized with acidic phosphorus compound

International Nuclear Information System (INIS)

Takeshita, Kenji; Nakano, Yoshio; Matsumura, Tatsuro

2001-01-01

A new gel-liquid extraction using a thermosensitive gel was proposed. The thermosensitive gel shows the conformational change of polymer network with temperature, which is known as the phase transition phenomena of gel. The extraction rate and equilibrium of Am(III) in an aqueous solution containing nitrate ion were measured batchwise by using a thermosensitive gel, N-isopropylacrylamide (NIPA) copolymerized with 2-methacryloyloxy- ethylacidphosphate (MR). The effects of the conformational change of polymer network on the extraction rate and equilibrium were discussed. The distribution ratio of Am(III) showed a large value at higher than LCST (low critical solution temperature; 34degC) and was decreased by the phase transition of gel from shrinking to swelling with decreasing temperature. The extraction of Am(III) in the aqueous solution and the release of Am(III) extracted in the gel were repeated stably by the temperature swing operation between 40 and 3degC. The extraction mechanism of Am(III) was described simply as Am 3+ + 3R - OH=(R-O) 3 Am + 3H + (R-OH: MR). The equilibrium constant at the shrinking state (40degC) was more than 3 times of that at swelling state (3degC). The gel-phase diffusivity of Eu(III) used as a substitute of Am(III) was evaluated as the order of 10 -12 m 2 /s at either of 3 or 40degC, which was similar to those for practical extraction chromatographic resins. The temperature-response of gel for the extraction of Eu(III) was very excellent without delay even for the rapid temperature change at 10degC/min. These results suggest that the extraction and release of Am(III) in an aqueous solution can be controlled by the conformational change of polymer network of thermosensitive gel. (author)

Experimental and theoretical studies on gas-phase reactions of NO3 radicals with three methoxyphenols: Guaiacol, creosol, and syringol

Science.gov (United States)

Yang, Bo; Zhang, Haixu; Wang, Youfeng; Zhang, Peng; Shu, Jinian; Sun, Wanqi; Ma, Pengkun

2016-01-01

Methoxyphenols, lignin pyrolysis products, are major biomass combustion components and are considered potential tracers for wood smoke emissions. Their atmospheric reactivity, however, has not been well characterized. Guaiacol, creosol, and syringol are three typical methoxyphenols generated in relatively high concentrations in fresh wood smoke. In this study, the gas-phase reactions of NO3 radicals with these methoxyphenols were investigated using a laboratory-built vacuum ultraviolet photoionization gas time-of-flight mass spectrometer (VUV-GTOFMS) and off-line GC-MS. By combining experimental and theoretical methods, 4-nitroguaiacol, 6-nitroguaiacol, and 4,6-dinitroguaiacol were determined as the primary degradation products for guaiacol; similarly, 6-nitrocreosol and 3-nitrosyringol were identified for creosol and syringol, respectively. Using the relative rate method, rate constants at 298 K and 1 atm for the gas-phase reactions of guaiacol, creosol, and syringol with NO3 radicals were measured to be 3.2 × 10-12, 2.4 × 10-13, and 4.0 × 10-13 cm3 molecule-1 s-1, respectively. At a typical tropospheric concentration of NO3 radicals (5 × 108 molecule cm-3), atmospheric lifetimes for guaiacol, creosol, and syringol toward NO3 radicals were 0.2, 2.3, and 1.4 h, respectively. These results indicate that the reaction with NO3 radicals can be a major sink for methoxyphenols at night.

Direct Reaction Experimental Studies with Beams of Radioactive Tin Ions

Energy Technology Data Exchange (ETDEWEB)

Jones, K. L. [University of Tennessee, Knoxville (UTK); Ahn, S.H. [University of Tennessee, Knoxville (UTK); Allmond, James M [ORNL; Ayres, A. [University of Tennessee, Knoxville (UTK); Bardayan, Daniel W [ORNL; Baugher, T. [Michigan State University, East Lansing; Bazin, D. [Michigan State University, National Superconducting Cyclotron Laboratory (NSCL); Beene, James R [ORNL; Berryman, J. S. [Michigan State University, East Lansing; Bey, A. [University of Tennessee, Knoxville (UTK); Bingham, C. R. [University of Tennessee, Knoxville (UTK); Cartegni, L. [University of Tennessee, Knoxville (UTK); Chae, K. Y. [University of Tennessee, Knoxville (UTK)/Sungkyunkwan University, Korea; Cizewski, J. A. [Rutgers University; Gade, A. [Michigan State University, National Superconducting Cyclotron Laboratory (NSCL); Galindo-Uribarri, Alfredo {nmn} [ORNL; Garcia-Ruiz, R.F. [Instituut voor Kernen Stralingsfysica, KU Leuven, B-3001, Leuven, Belgium; Grzywacz, Robert Kazimierz [ORNL; Howard, Meredith E [ORNL; Kozub, R. L. [Tennessee Technological University (TTU); Liang, J Felix [ORNL; Manning, Brett M [ORNL; Matos, M. [Louisiana State University; McDaniel, S. [Michigan State University, East Lansing; Miller, D. [University of Tennessee, Knoxville (UTK); Nesaraja, Caroline D [ORNL; O' Malley, Patrick [Rutgers University; Padgett, S [University of Tennessee, Knoxville (UTK); Padilla-Rodal, Elizabeth [Universidad Nacional Autonoma de Mexico (UNAM); Pain, Steven D [ORNL; Pittman, S. T. [University of Tennessee (UTK) and Oak Ridge National Laboratory (ORNL); Radford, David C [ORNL; Ratkiewicz, Andrew J [ORNL; Schmitt, Kyle [ORNL; Smith, Michael Scott [ORNL; Stracener, Daniel W [ORNL; Stroberg, S. [Michigan State University, East Lansing; Tostevin, Jeffrey A [ORNL; Varner Jr, Robert L [ORNL; Weisshaar, D. [Michigan State University, East Lansing; Wimmer, K. [Michigan State University, National Superconducting Cyclotron Laboratory (NSCL)/Central Michigan University; Winkler, R. [Michigan State University, East Lansing

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.

The development and experimental validation of a reduced ternary kinetic mechanism for the auto-ignition at HCCI conditions, proposing a global reaction path for ternary gasoline surrogates

Energy Technology Data Exchange (ETDEWEB)

Machrafi, Hatim; Cavadias, Simeon; Amouroux, Jacques [UPMC Universite Paris 06, LGPPTS, Ecole Nationale Superieure de Chimie de Paris, 11, rue de Pierre et Marie Curie, 75005 Paris (France)

2009-02-15

To acquire a high amount of information of the behaviour of the Homogeneous Charge Compression Ignition (HCCI) auto-ignition process, a reduced surrogate mechanism has been composed out of reduced n-heptane, iso-octane and toluene mechanisms, containing 62 reactions and 49 species. This mechanism has been validated numerically in a 0D HCCI engine code against more detailed mechanisms (inlet temperature varying from 290 to 500 K, the equivalence ratio from 0.2 to 0.7 and the compression ratio from 8 to 18) and experimentally against experimental shock tube and rapid compression machine data from the literature at pressures between 9 and 55 bar and temperatures between 700 and 1400 K for several fuels: the pure compounds n-heptane, iso-octane and toluene as well as binary and ternary mixtures of these compounds. For this validation, stoichiometric mixtures and mixtures with an equivalence ratio of 0.5 are used. The experimental validation is extended by comparing the surrogate mechanism to experimental data from an HCCI engine. A global reaction pathway is proposed for the auto-ignition of a surrogate gasoline, using the surrogate mechanism, in order to show the interactions that the three compounds can have with one another during the auto-ignition of a ternary mixture. (author)

Chitosan Derivatives: Introducing New Functionalities with a Controlled Molecular Architecture for Innovative Materials

Directory of Open Access Journals (Sweden)

Waldo M. Argüelles-Monal

2018-03-01

Full Text Available The functionalization of polymeric substances is of great interest for the development of innovative materials for advanced applications. For many decades, the functionalization of chitosan has been a convenient way to improve its properties with the aim of preparing new materials with specialized characteristics. In the present review, we summarize the latest methods for the modification and derivatization of chitin and chitosan under experimental conditions, which allow a control over the macromolecular architecture. This is because an understanding of the interdependence between chemical structure and properties is an important condition for proposing innovative materials. New advances in methods and strategies of functionalization such as the click chemistry approach, grafting onto copolymerization, coupling with cyclodextrins, and reactions in ionic liquids are discussed.

Characterization of PE-g-HEMA films prepared by gamma irradiation through nuclear microprobe techniques

International Nuclear Information System (INIS)

Ferreira, L.M.; Rodrigues, P.A.; Falcao, A.N.; Leal, J.P.

2011-01-01

Complete text of publication follows. The functional success of a copolymer as biomaterial depends fundamentally on their mechanical properties (stemming from the material matrix) and on the characteristics of its surface. For biomedical applications, among all the other important properties, the biocompatibility of the surface acquires extreme importance and can dictate its rejection. One of the issues regarding biocompatibility is cytotoxicity which strongly depends on the contamination level at surface. Ion beam analysis techniques associated to Nuclear Microprobe (PIXE, RBS and STIM) allows a rigorous and precise analysis of the concentration (ppm) and distribution of elements contamination, and may also provide information on its near-surface structure. In this work PE-g-HEMA films with different grafting yields were prepared by mutual gamma irradiation at a 60 Co source and were analyzed through nuclear microprobe. Data collected allowed the qualitative and quantitative evaluation of contaminants distribution observed in the different samples as well as the clarification of some processes occurred during the copolymerization reaction. Qualitative analysis showed a random and no homogeneous distribution of the contaminant elements, independent of the grafting degree, suggesting the existence of several sources of contamination at different stages of their preparation. Results also suggest that this 'phased' contamination occurs simultaneously with mechanisms of agglomeration/entrapment of impurities during the gamma induced copolymerization reaction. Moreover, quantitative data showed that all contaminants found in the copolymeric films are natural contaminants of their reagents of preparation, although at concentrations without toxicological hazard, which points to a low cytotoxic potential. The combined analysis of these data with data from SEM and AFM allowed a better understanding of the surface structure and other properties already observed in these

Optimizing Chemical Reactions with Deep Reinforcement Learning.

Science.gov (United States)

Zhou, Zhenpeng; Li, Xiaocheng; Zare, Richard N

2017-12-27

Deep reinforcement learning was employed to optimize chemical reactions. Our model iteratively records the results of a chemical reaction and chooses new experimental conditions to improve the reaction outcome. This model outperformed a state-of-the-art blackbox optimization algorithm by using 71% fewer steps on both simulations and real reactions. Furthermore, we introduced an efficient exploration strategy by drawing the reaction conditions from certain probability distributions, which resulted in an improvement on regret from 0.062 to 0.039 compared with a deterministic policy. Combining the efficient exploration policy with accelerated microdroplet reactions, optimal reaction conditions were determined in 30 min for the four reactions considered, and a better understanding of the factors that control microdroplet reactions was reached. Moreover, our model showed a better performance after training on reactions with similar or even dissimilar underlying mechanisms, which demonstrates its learning ability.

Effects of electrostatic interactions on electron transfer reactions

International Nuclear Information System (INIS)

Hickel, B.

1987-01-01

The fast reactions of electron transfer are studied by pulse radiolysis. This technique allows the creation in about 10 -8 second radicals and radical ions with high redox potentials. For solvated electrons electrostatic interaction on the kinetics of reactions limited by diffusion is described by Debye's equation when ion mobility is known. Deviation from theory can occur in ion pairs formation. This is evidenced experimentally for anions by cation complexation with a cryptate. Relatively slow reactions are more sensitive to electrostatic interactions than limited by diffusion. If ion pairs are not formed kinetics constant depends on dielectric constant of solvent and reaction radius. Experimentally is studied the effect of electrostatic interaction on the rate constants of solvated electrons with anions and cations in water-ethanol mixtures where the dielectric constant change from 80 to 25 at room temperature. 17 refs

Quasi-elastic reactions: an interplay of reaction dynamics and nuclear structure

Directory of Open Access Journals (Sweden)

Recchia F.

2011-10-01

Full Text Available Multinucleon transfer reactions have been investigated in 40Ar+208Pb with the Prisma+Clara set-up. The experimental differential cross sections of different neutron transfer channels have been obtained at three different angular settings taking into account the transmission through the spectrometer. The experimental yields of the excited states have been determined via particle-γ coincidences. In odd Ar isotopes, we reported a signif cant population of 11/2− states, reached via neutron transfer. Their structure matches a stretched conf guration of the valence neutron coupled to vibration quanta.

Spallation reactions - physics and applications

International Nuclear Information System (INIS)

Kelic, A.; Ricciardi, M.; Schmidt, K-H.

2009-01-01

Spallation reactions have become an ideal tool for studying the equation of state and thermal instabilities of nuclear matter. In astrophysics, the interactions of cosmic rays with the interstellar medium have to be understood in detail for deducing their original composition and their production mechanisms. Renewed interest in spallation reactions with protons around 1 GeV came up recently with the developments of spallation neutron sources. The project of an accelerator-driven system (ADS) as a technological solution for incinerating the radioactive waste even intensified the efforts for better understanding the physics involved in the spallation process. Experiments on spallation reactions were performed for determining the production cross sections and properties of particles, fragments and heavy residues. Traditional experiments on heavy residues, performed in direct kinematics, were limited to the direct observation of long-lived radioactive nuclides and did not provide detailed information on the kinematics of the reaction. Therefore, an innovative experimental method has been developed, based on inverse kinematics, which allowed to identify all reaction residues in-flight, using the high resolution magnetic spectrometer FRS of GSL Darmstadt. It also gives direct access to the reaction kinematics. An experimental campaign has been carried out in a Europe-wide collaboration, investigating the spallation of several nuclei ranging from 56 Fe to 238 U Complementary experiments were performed with a full-acceptance detection system, yielding total fission cross sections. Recently, another detection system using the large acceptance ALADIN dipole and the LAND neutron detector was introduced to measure light particles in coincidence with the heavy residues. Another intense activity was dedicated to developing codes, which cover nuclear reactions occurring in an ADS. The first phase of the reaction is successfully described by a sequence of quasi-free nucleon

Using Central Composite Experimental Design to Optimize the Degradation of Tylosin from Aqueous Solution by Photo-Fenton Reaction

Directory of Open Access Journals (Sweden)

Abd Elaziz Sarrai

2016-05-01

Full Text Available The feasibility of the application of the Photo-Fenton process in the treatment of aqueous solution contaminated by Tylosin antibiotic was evaluated. The Response Surface Methodology (RSM based on Central Composite Design (CCD was used to evaluate and optimize the effect of hydrogen peroxide, ferrous ion concentration and initial pH as independent variables on the total organic carbon (TOC removal as the response function. The interaction effects and optimal parameters were obtained by using MODDE software. The significance of the independent variables and their interactions was tested by means of analysis of variance (ANOVA with a 95% confidence level. Results show that the concentration of the ferrous ion and pH were the main parameters affecting TOC removal, while peroxide concentration had a slight effect on the reaction. The optimum operating conditions to achieve maximum TOC removal were determined. The model prediction for maximum TOC removal was compared to the experimental result at optimal operating conditions. A good agreement between the model prediction and experimental results confirms the soundness of the developed model.

Ion-molecular reactions initiated by β-decay of tritium in tritiated compounds

International Nuclear Information System (INIS)

Akulov, G.P.

1976-01-01

Ion-molecular reactions initiated by β-decay of tritium and tritiated hydrocarbons have been systematized. The review describes the theoretical and experimental foundation of the radiochemical method of this important type of chemical interactions investigation. The reactions of the molecular ions of HeT + with methane, ethane, propane, butane and also with cycloalkanes from C 3 to C 6 are discussed. The reactions under consideration have been united into two groups: reactions involving HeT + ions and those involving carbonic ions. From the experimental results available, the conclusions have been drawn about the reactivity of these intermediate formations, about the mechanism of their interaction with organic substances, and also about the perspectives of using the radiochemical method in studies of ion-molecular reactions. The experimental results published before May 1974 are examined. The bibliography includes 162 references

Coupled enzyme reactions performed in heterogeneous reaction media: experiments and modeling for glucose oxidase and horseradish peroxidase in a PEG/citrate aqueous two-phase system.

Science.gov (United States)

Aumiller, William M; Davis, Bradley W; Hashemian, Negar; Maranas, Costas; Armaou, Antonios; Keating, Christine D

2014-03-06

The intracellular environment in which biological reactions occur is crowded with macromolecules and subdivided into microenvironments that differ in both physical properties and chemical composition. The work described here combines experimental and computational model systems to help understand the consequences of this heterogeneous reaction media on the outcome of coupled enzyme reactions. Our experimental model system for solution heterogeneity is a biphasic polyethylene glycol (PEG)/sodium citrate aqueous mixture that provides coexisting PEG-rich and citrate-rich phases. Reaction kinetics for the coupled enzyme reaction between glucose oxidase (GOX) and horseradish peroxidase (HRP) were measured in the PEG/citrate aqueous two-phase system (ATPS). Enzyme kinetics differed between the two phases, particularly for the HRP. Both enzymes, as well as the substrates glucose and H2O2, partitioned to the citrate-rich phase; however, the Amplex Red substrate necessary to complete the sequential reaction partitioned strongly to the PEG-rich phase. Reactions in ATPS were quantitatively described by a mathematical model that incorporated measured partitioning and kinetic parameters. The model was then extended to new reaction conditions, i.e., higher enzyme concentration. Both experimental and computational results suggest mass transfer across the interface is vital to maintain the observed rate of product formation, which may be a means of metabolic regulation in vivo. Although outcomes for a specific system will depend on the particulars of the enzyme reactions and the microenvironments, this work demonstrates how coupled enzymatic reactions in complex, heterogeneous media can be understood in terms of a mathematical model.

Contribution to an effective design method for stationary reaction-diffusion patterns

International Nuclear Information System (INIS)

Szalai, István; Horváth, Judit; De Kepper, Patrick

2015-01-01

The British mathematician Alan Turing predicted, in his seminal 1952 publication, that stationary reaction-diffusion patterns could spontaneously develop in reacting chemical or biochemical solutions. The first two clear experimental demonstrations of such a phenomenon were not made before the early 1990s when the design of new chemical oscillatory reactions and appropriate open spatial chemical reactors had been invented. Yet, the number of pattern producing reactions had not grown until 2009 when we developed an operational design method, which takes into account the feeding conditions and other specificities of real open spatial reactors. Since then, on the basis of this method, five additional reactions were shown to produce stationary reaction-diffusion patterns. To gain a clearer view on where our methodical approach on the patterning capacity of a reaction stands, numerical studies in conditions that mimic true open spatial reactors were made. In these numerical experiments, we explored the patterning capacity of Rabai's model for pH driven Landolt type reactions as a function of experimentally attainable parameters that control the main time and length scales. Because of the straightforward reversible binding of protons to carboxylate carrying polymer chains, this class of reaction is at the base of the chemistry leading to most of the stationary reaction-diffusion patterns presently observed. We compare our model predictions with experimental observations and comment on agreements and differences

Contribution to an effective design method for stationary reaction-diffusion patterns

Energy Technology Data Exchange (ETDEWEB)

Szalai, István; Horváth, Judit [Laboratory of Nonlinear Chemical Dynamics, Institute of Chemistry, Eötvös Loránd University, P.O. Box 32, H-1518 Budapest 112 (Hungary); De Kepper, Patrick [Centre de Recherche Paul Pascal, CNRS, University of Bordeaux, 115, Avenue Schweitzer, F-33600 Pessac (France)

2015-06-15

The British mathematician Alan Turing predicted, in his seminal 1952 publication, that stationary reaction-diffusion patterns could spontaneously develop in reacting chemical or biochemical solutions. The first two clear experimental demonstrations of such a phenomenon were not made before the early 1990s when the design of new chemical oscillatory reactions and appropriate open spatial chemical reactors had been invented. Yet, the number of pattern producing reactions had not grown until 2009 when we developed an operational design method, which takes into account the feeding conditions and other specificities of real open spatial reactors. Since then, on the basis of this method, five additional reactions were shown to produce stationary reaction-diffusion patterns. To gain a clearer view on where our methodical approach on the patterning capacity of a reaction stands, numerical studies in conditions that mimic true open spatial reactors were made. In these numerical experiments, we explored the patterning capacity of Rabai's model for pH driven Landolt type reactions as a function of experimentally attainable parameters that control the main time and length scales. Because of the straightforward reversible binding of protons to carboxylate carrying polymer chains, this class of reaction is at the base of the chemistry leading to most of the stationary reaction-diffusion patterns presently observed. We compare our model predictions with experimental observations and comment on agreements and differences.

Annual report on experimental operations and maintenances of mock-up model test facility with a full-scale reaction tube for HTTR hydrogen production system in 2003 fiscal year (Contract research)

International Nuclear Information System (INIS)

Hayashi, Koji; Morisaki, Norihiro; Ohashi, Hirofumi; Kato, Michio; Aita, Hideki; Takeda, Tetsuaki; Nishihara, Tetsuo; Inaba, Yoshitomo; Takada, Shoji; Inagaki, Yoshiyuki

2006-03-01

This is a report on the experimental operations and maintenances of the mock-up test facility with a full-scale reaction tube for the HTTR hydrogen production system in 2003 fiscal year. The fourth and fifth experimental test operations were performed, from May to July and from October to December in 2003, for the following tests; (a) start-up and shutdown operation test, (b) process change test, (c) continuous hydrogen-production test and (d) chemical reaction shutdown test. From the results, a long time-range stability of the hydrogen production system was confirmed, a behavior of the helium-gas cooling system, consists of steam generator and radiator; during chemical reaction shutdown, was understood, and so on. Periodic inspections on boiler equipment and high-pressure gas production facilities were performed from end of July 2003. This report is summarized on outlines and results of the tests, outlines and results of the periodic inspections, and operation records of the mock-up test facility. (author)

Monotectic four-phase reaction in Al-Bi-Zn alloys

Energy Technology Data Exchange (ETDEWEB)

Groebner, J. [Clausthal University of Technology, Institute of Metallurgy, Robert-Koch-Str. 42, D-38678 Clausthal-Zellerfeld (Germany); Mirkovic, D. [Clausthal University of Technology, Institute of Metallurgy, Robert-Koch-Str. 42, D-38678 Clausthal-Zellerfeld (Germany); Schmid-Fetzer, R. [Clausthal University of Technology, Institute of Metallurgy, Robert-Koch-Str. 42, D-38678 Clausthal-Zellerfeld (Germany)]. E-mail: schmid-fetzer@tu-clausthal.de

2005-06-15

Thermodynamic phase diagram calculations were used for the systematic search for a monotectic four-phase reaction in ternary Al-alloys. Systems with intermetallic phases and also the elements Cd and Hg were excluded in the present search. The ternary Al-Bi-Zn is a rare occasion where such a reaction, L' = L' + (Al)' + (Zn), actually occurs. Experimental work could be focused on key samples in that system and involved DSC for thermal analysis and calorimetry, and also metallographic analysis using SEM/EDX. Experimental results verify the existence of the monotectic reaction and were also used for a quantitative thermodynamic modeling of Al-Bi-Zn. Solidification paths and microstructures of Al-Bi-Zn alloys are shown to be rather complex. Using thermodynamic calculations, these rich details involving up to three invariant reactions and unexpected monovariant reaction types can be clearly revealed and understood.

Analysis of reaction cross-section production in neutron induced fission reactions on uranium isotope using computer code COMPLET.

Science.gov (United States)

Asres, Yihunie Hibstie; Mathuthu, Manny; Birhane, Marelgn Derso

2018-04-22

This study provides current evidence about cross-section production processes in the theoretical and experimental results of neutron induced reaction of uranium isotope on projectile energy range of 1-100 MeV in order to improve the reliability of nuclear stimulation. In such fission reactions of 235 U within nuclear reactors, much amount of energy would be released as a product that able to satisfy the needs of energy to the world wide without polluting processes as compared to other sources. The main objective of this work is to transform a related knowledge in the neutron-induced fission reactions on 235 U through describing, analyzing and interpreting the theoretical results of the cross sections obtained from computer code COMPLET by comparing with the experimental data obtained from EXFOR. The cross section value of 235 U(n,2n) 234 U, 235 U(n,3n) 233 U, 235 U(n,γ) 236 U, 235 U(n,f) are obtained using computer code COMPLET and the corresponding experimental values were browsed by EXFOR, IAEA. The theoretical results are compared with the experimental data taken from EXFOR Data Bank. Computer code COMPLET has been used for the analysis with the same set of input parameters and the graphs were plotted by the help of spreadsheet & Origin-8 software. The quantification of uncertainties stemming from both experimental data and computer code calculation plays a significant role in the final evaluated results. The calculated results for total cross sections were compared with the experimental data taken from EXFOR in the literature, and good agreement was found between the experimental and theoretical data. This comparison of the calculated data was analyzed and interpreted with tabulation and graphical descriptions, and the results were briefly discussed within the text of this research work. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Co-solvent effects on reaction rate and reaction equilibrium of an enzymatic peptide hydrolysis.

Science.gov (United States)

Wangler, A; Canales, R; Held, C; Luong, T Q; Winter, R; Zaitsau, D H; Verevkin, S P; Sadowski, G

2018-04-25

This work presents an approach that expresses the Michaelis constant KaM and the equilibrium constant Kth of an enzymatic peptide hydrolysis based on thermodynamic activities instead of concentrations. This provides KaM and Kth values that are independent of any co-solvent. To this end, the hydrolysis reaction of N-succinyl-l-phenylalanine-p-nitroanilide catalysed by the enzyme α-chymotrypsin was studied in pure buffer and in the presence of the co-solvents dimethyl sulfoxide, trimethylamine-N-oxide, urea, and two salts. A strong influence of the co-solvents on the measured Michaelis constant (KM) and equilibrium constant (Kx) was observed, which was found to be caused by molecular interactions expressed as activity coefficients. Substrate and product activity coefficients were used to calculate the activity-based values KaM and Kth for the co-solvent free reaction. Based on these constants, the co-solvent effect on KM and Kx was predicted in almost quantitative agreement with the experimental data. The approach presented here does not only reveal the importance of understanding the thermodynamic non-ideality of reactions taking place in biological solutions and in many technological applications, it also provides a framework for interpreting and quantifying the multifaceted co-solvent effects on enzyme-catalysed reactions that are known and have been observed experimentally for a long time.

Multiparticle production in heavy-ion reactions

International Nuclear Information System (INIS)

Pelte, D.

1980-01-01

This lecture is concerned with the question how many particles and what kind of them are produced in heavy-ion collisions at energies about 10 MeV/n. We tend to assume that heavy-ion reactions at this energy are binary reactions. The experimental set consisting of two large ionization chambers serving to detection, in coincidence, the reaction fragments is described. With this set-up a number of reactions induced on 27 Al, 28 Si and 40 Ca by the 32 S beam of 135 and 190 MeV energy has been studied. Two-fragments inclusive and exclusive reactions were investigated. The assumption of a sequential statistical decay gives the best agreement with the data for all analyzed cases. (H.M.)

Radiation-sensitive compounds and methods of using same

International Nuclear Information System (INIS)

DeMajistre, R.

1977-01-01

Novel diacrylates are prepared by reacting a monohydroxylated acrylic monomer with a polyisocyanate. The reaction product may be polymerized by subjecting to ionizing irradiation, actinic light or to free radical catalysis to form a useful coating material. The diacrylates may also be copolymerized with other radiation sensitive materials

Infrared laser-induced chemical reactions

International Nuclear Information System (INIS)

Katayama, Mikio

1978-01-01

The experimental means which clearly distinguishes between infrared ray-induced reactions and thermal reactions has been furnished for the first time when an intense monochromatic light source has been obtained by the development of infrared laser. Consequently, infrared laser-induced chemical reactions have started to develop as one field of chemical reaction researches. Researches of laser-induced chemical reactions have become new means for the researches of chemical reactions since they were highlighted as a new promising technique for isotope separation. Specifically, since the success has been reported in 235 U separation using laser in 1974, comparison of this method with conventional separation techniques from the economic point of view has been conducted, and it was estimated by some people that the laser isotope separation is cheaper. This report briefly describes on the excitation of oscillation and reaction rate, and introduces the chemical reactions induced by CW laser and TEA CO 2 laser. Dependence of reaction yield on laser power, measurement of the absorbed quantity of infrared ray and excitation mechanism are explained. Next, isomerizing reactions are reported, and finally, isotope separation is explained. It was found that infrared laser-induced chemical reactions have the selectivity for isotopes. Since it is evident that there are many examples different from thermal and photo-chemical reactions, future collection of the data is expected. (Wakatsuki, Y.)

Ergonomic office design and aging: a quasi-experimental field study of employee reactions to an ergonomics intervention program.

Science.gov (United States)

May, Douglas R; Reed, Kendra; Schwoerer, Catherine E; Potter, Paul

2004-04-01

A naturally occurring quasi-experimental longitudinal field study of 87 municipal employees using pretest and posttest measures investigated the effects of an office workstation ergonomics intervention program on employees' perceptions of their workstation characteristics, levels of persistent pain, eyestrain, and workstation satisfaction. The study examined whether reactions differed between younger and older employees. Results revealed that workstation improvements were associated with enhanced perceptions of the workstation's ergonomic qualities, less upper back pain, and greater workstation satisfaction. Among those experiencing an improvement, the perceptions of workstation ergonomic qualities increased more for younger than older employees, supporting the "impressionable years" framework in the psychological literature on aging. Implications for human resources managers are discussed.

Ozonization, Amination and Photoreduction of Graphene Oxide for Triiodide Reduction Reaction: An Experimental and Theoretical Study

International Nuclear Information System (INIS)

Jing, Hongyu; Ren, Suzhen; Shi, Yantao; Song, Xuedan; Yang, Ying; Guo, Yanan; An, Yonglin; Hao, Ce

2017-01-01

This work proposes a mild and environmentally-friendly approach to prepare a highly efficient functional graphene (termed as AGO-hv) using methods of ozone oxidation, solvothermal synthesis, and photoreduction. The use of ozone oxidation in the first step can effectively increase the interlaminar distance between graphite oxide sheets, and create active sites for nucleophilic attack on the epoxy carbon from ammonia. The amino groups were successfully grafted on the surface of graphene as evidenced by the amidation reaction, with a maximum nitrogen content of 10.46 wt% and a C/N molar ratio of 8.46. After further photoreduction of the aminated graphite oxide (AGO), the residual oxygen functionalities, such as C-OH, were effectively removed and the conductivity of the graphene sheet was further recovered. The dye-sensitized solar cell (DSC) exhibited a power conversion efficiency (PCE) of 7.51% based on AGO-hv counter electrode (CE), close to that of Pt counterpart (7.79%). The experimental results indicated that the amidation and photoreduction processes were significantly facilitated by the initial ozonization of graphene oxide, and this process significantly improved the electrochemical activity and the conductivity of graphene oxide. Density functional theory (DFT) calculations revealed that AGO-hv had the lowest ionization energy (a better electron-donating ability) and also suitable binding energy with I atoms as well. The combination of ozonization, amination and photoreduction is an efficient route to obtain electrocatalysts with desired compositional distributions and performance for triiodide reduction reaction in DSCs.

Multiple heavy-fragment breakup reactions

International Nuclear Information System (INIS)

Pelte, D.

1986-01-01

Data for heavy ion breakup reactions for projectiles between silicon 28 and argon 40 and targets between carbon 12 and zirconium 90 in the energy range 7 to 15 MeV/n are presented. The experimental method used to cope with the complexity of the exit channels in these reactions is discussed. Data on cross sections, isotopic distribution, charge distribution, energy dependence, Q-value and angular momentum of the target are discussed in relationship to model predictions

Polar Diels-Alder reactions using electrophilic nitrobenzothiophenes. A combined experimental and DFT study

Science.gov (United States)

Della Rosa, Claudia D.; Mancini, Pedro M. E.; Kneeteman, Maria N.; Lopez Baena, Anna F.; Suligoy, Melisa A.; Domingo, Luis R.

2015-01-01

The reactions between 2- and 3-nitrobenzothiophenes with three dienes of different nucleophilicity, 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, 1-trimethylsilyloxy-1,3-butadiene and isoprene developed in anhydrous benzene and alternative under microwave irradiation with molecular solvents or in free solvent conditions, respectively, for produce dibenzothiophenes permit to conclude that both nitroheterocycles act as electrophile with the cited dienes. In the cases of the dienes 1-methoxy-3-trimethylsilyloxy-1,3-butadiene and 1-trimethylsilyloxy-1,3-butadiene which posses major nucleophilicity the observed product is the normal cycloaddition one. However when the diene is isoprene the product with both electrophiles follow the hetero Diels-Alder way. These reactions are considered polar cycloaddition reactions and the yields are reasonables. Moreover the polar Diels-Alder reactions of nitrobenzothiophenes with electron rich dienes 1-trimethylsilyloxy-1,3-butadiene have been theoretically studied using DFT methods.

Tri-n-Butylborane/WaterComplex-Mediated Copolymerization of Methyl Methacrylate with Proteinaceous Materials and Proteins: A Review

Directory of Open Access Journals (Sweden)

Yoshinori Kadoma

2010-11-01

Full Text Available Previous studies of tri-n-butylborane–initiated graft copolymerization of methyl methacrylates with hydrated proteinous materials and proteins have focused on the number of grafted-poly (MMA branches as well as the percent graft and graft efficiency. The number of branches in silk fibroin is 1.3, whereas the number in collagen, gelatin, ovalbumin and wool are 0.1, 0.04, 0.02 and 0.03, respectively. The number of grafted-PMMA branches in synthetic poly-L-peptides is approximately 10-fold less than that in gelatin, and decline, in the order poly-Ala > poly-Ser > poly-Pro > poly-Glu > poly-Lys. By contrast, poly-Gly, poly-Tyr and poly-Leu have no branches. The co-catalytic effect (the ratio of the number of polymer formed relative to that of control of amino acids on tri-n-butylborane-initiated polymerization of MMA in the presence of water has been linearly correlated with their ionization potential (IPkoopman; |Äå HOMO (Highest Occupied Molecular Orbital| (r2 = 0.6, outliers: Cys and His; Äå HOMO = [åHOMOaqua − åHOMOvacuum] calculated using the semiempirical AM1 method. Also, a significant exponential relationship between the number of branches of poly-L-polypeptides and the Äå HOMO of the corresponding amino acids has been observed (r2 = 0.9. A possible grafting site of protein (polypeptide is discussed.

Experimental Study on Impact-Induced Reaction Characteristics of PTFE/Ti Composites Enhanced by W Particles

Directory of Open Access Journals (Sweden)

Yan Li

2017-02-01

Full Text Available Metal/fluoropolymer composites are a category of energetic structural materials that release energy through exothermic chemical reactions initiated under highly dynamic loadings. In this paper, the chemical reaction mechanism of PTFE (polytetrafluoroethylene/Ti/W composites is investigated through thermal analysis and composition analysis. These composites undergo exothermic reactions at 510 °C to 600 °C, mainly producing TiFx. The tungsten significantly reduces the reaction heat due to its inertness. In addition, the dynamic compression properties and impact-induced reaction behaviors of PTFE/Ti/W composites with different W content prepared by pressing and sintering are studied using Split Hopkinson Pressure Bar and high speed photography. The results show that both the mechanical strength and the reaction degree are significantly improved with the increasing strain rate. Moreover, as W content increases, the mechanical strength is enhanced, but the elasticity/plasticity is decreased. The PTFE/Ti/W composites tend to become more inert with the increasing W content, which is reflected by the reduced reaction degree and the increased reaction threshold for the impact ignition.

Reaction rate of 24Mg(p,γ)25Al

International Nuclear Information System (INIS)

Powell, D.C.; Iliadis, C.; Champagne, A.E.; Grossmann, C.A.; Hale, S.E.; Hansper, V.Y.; McLean, L.K.

1999-01-01

The proton-capture reaction on 24 Mg has been investigated in the bombarding energy range of E p =0.2-1.7 MeV. Resonance properties (strengths, branching ratios and lifetimes) of low-energy resonances have been measured. From the experimental results, accurate proton partial widths, γ-ray partial widths and total widths (Γ p , Γ γ , and Γ) have been deduced. The present experimental information establishes the 24 Mg+p reaction rates over the temperature range T=0.02-2.0 GK with statistical uncertainties of 5% to 21%. Our recommended reaction rates deviate from previous estimates by 18% to 45%. Based on our results, we can rule out the recent suggestion that the total width of the E R =223 keV resonance has a significant influence on the reaction rates. We also discuss several effects that might give rise to systematic uncertainties in the reaction rates. The astrophysical implications for hydrogen burning of 24 Mg at low stellar temperatures are presented

Exchange reaction between hydrogen and deuterium. I. Importance of surface reactions in the steady-state mechanism

Energy Technology Data Exchange (ETDEWEB)

Marteau, C; Gaillard-Cusin, F; James, H [Centre National de la Recherche Scientifique, 45 - Orleans-la-Source (France). Centre de Recherches sur la Chimie de Combustion et des Hautes Temperatures

1978-05-01

Investigation of heterogeneous initiation process of gas phase linear chain reactions is carried out through the study of H/sub 2/-D/sub 2/ exchange reaction. Experimental data under study concern mainly the stationary rate of HD formation and the prestationary proceeding. Steady-state method accounts for the first one of these data; it allows to clearly compare the wall process part to the part played by the homogeneous chain reaction towards HD formation. Activation energy of exchange elementary step between chemisorbed hydrogen (on silica) and gaseous deuterium has been evaluated: Esub(e1)=52+-1 Kcal/mole.

Activation barriers for series of exothermic homologous reactions. VI. Reactions of lanthanide and transition metal atoms.

Science.gov (United States)

Blue, Alan S.; Fontijn, Arthur

2001-09-01

Semiempirical configuration interaction (SECI) theory to predict activation barriers, E, as given by k(T)=ATn exp(-E(RT), has been applied to homologous series of lanthanide (LN) and transition metal (TM) atom oxidation reactions. This was achieved by considering as homologous series reactions of elements differing only by the number of electrons in one subshell. Comparison between SECI and experimental results leads to an average deviation for the LN+N2O reactions of 0.66 kJ mol-1, and up to 5.5 kJ mol-1 for other series. Thirty-one activation barriers are reported.

1,3,5-Triethylbenzene Transformation Reactions Compared to Its Transalkylation Reaction with Ethylbenzene

KAUST Repository

Akhtar, M. Naseem; Sulaiman, Al Khattaf

2009-01-01

The transalkylation of 1,3,5-triethylbenzene (1,3,5-TEB) with ethylbenzene (EB) has been studied over USYtype catalysts using a riser simulator that mimics the operation of a fluidized-bed reactor. The reaction mixture EB and 1,3,5-TEB was used at a molar ratio of 1:1, which is equivalent to 40:60 wt % of EB/1,3,5-TEB, respectively. The reaction temperature was varied from 350 to 500 °C with a time on stream ranging from 3-15 s. The effect of reaction conditions on 1,3,5-TEB conversion, DEB selectivity, and isomerization of 1,3,5-TEB is reported. The transalkylation of 1,3,5-TEB with EB has been compared to the transformation reaction of pure 1,3,5-TEB and EB. The experimental results have revealed that reactivity of 1,3,5-TEB and selectivity of DEB is increased during the transalkylation reaction (EB + 1,3,5-TEB) as compared to the transformation reaction of pure EB or 1,3,5-TEB. The 1,3,5-TEB undergoes isomerization and a cracking reaction to produce DEB and EB but does not undergo any appreciable disproportionation reaction. The isomerization of 1,3,5-TEB is more active at low temperatures, while cracking is more active at high temperatures. © 2009 American Chemical Society.

1,3,5-Triethylbenzene Transformation Reactions Compared to Its Transalkylation Reaction with Ethylbenzene

KAUST Repository

Akhtar, M. Naseem

2009-08-20

The transalkylation of 1,3,5-triethylbenzene (1,3,5-TEB) with ethylbenzene (EB) has been studied over USYtype catalysts using a riser simulator that mimics the operation of a fluidized-bed reactor. The reaction mixture EB and 1,3,5-TEB was used at a molar ratio of 1:1, which is equivalent to 40:60 wt % of EB/1,3,5-TEB, respectively. The reaction temperature was varied from 350 to 500 °C with a time on stream ranging from 3-15 s. The effect of reaction conditions on 1,3,5-TEB conversion, DEB selectivity, and isomerization of 1,3,5-TEB is reported. The transalkylation of 1,3,5-TEB with EB has been compared to the transformation reaction of pure 1,3,5-TEB and EB. The experimental results have revealed that reactivity of 1,3,5-TEB and selectivity of DEB is increased during the transalkylation reaction (EB + 1,3,5-TEB) as compared to the transformation reaction of pure EB or 1,3,5-TEB. The 1,3,5-TEB undergoes isomerization and a cracking reaction to produce DEB and EB but does not undergo any appreciable disproportionation reaction. The isomerization of 1,3,5-TEB is more active at low temperatures, while cracking is more active at high temperatures. © 2009 American Chemical Society.

Interfacial reactions in intermetallic matrix composites

International Nuclear Information System (INIS)

Cantrell, L.B.; Clevenger, E.M.; Perepezko, J.H.

1993-01-01

The thermal stability of advanced composites is dominated by the behavior of internal interfaces. Analysis of these internal interfaces often involves consideration of at least ternary order phase equilibria. Limited thermodynamic data exists for ternary and higher order systems. However, a combined approach based upon the use of binary data to estimate ternary phase equilibria and experimentally determined reaction pathways is effective in the analysis of interface reactions in composite systems. In blended powder samples, thermal analysis was used to find possible reaction temperatures, while X-ray analysis, EDS, and EPMA of diffusion couples were used to assess interdiffusion reaction pathways. The approach is illustrated by compatibility studies between TiAl and TiSi 2 at 1,100 C, and in-situ reactions between B 4 C and TiAl at 1300 C where multiple reaction sequences have been analyzed to provide guidance for the design of in-situ reaction processing of composites

Stabilitas emulsi kopolimer S-GMA (stirena – glisidil metakrilat

Directory of Open Access Journals (Sweden)

Isananto Winursito

1992-08-01

Full Text Available Epoxy groups in glycidyl methacrylate (GMA units have been available for the reaction with amine of proteins or other biological active substrates to prepare biomaterials and hybrid devices. Soap-soap copolymerization of GMA with styrene (S result the formation of stable latex. Hydrolysis of epoxy groups in copolymer particles increased emulsion stability. The effect of pH, temperature and reaction time in the hydrolysis of S-GMA copolymer have been investigated.

Micellar copolymerization of poly(acrylamide-g-propylene oxide): rheological evaluation and solution characterization; Copolimerizacao micelar de poli(acrilamida-g-oxido de propileno): avaliacao reologica e caracterizacao de suas solucoes

Energy Technology Data Exchange (ETDEWEB)

Sadicoff, Bianca L.; Brandao, Edimir M.; Lucas, Elizabete F. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Inst. de Macromoleculas]. E-mail: elucas@ima.ufrj.br; Amorim, Marcia C.V. [Universidade Estadual, Rio de Janeiro, RJ (Brazil). Inst. de Quimica

2001-06-01

Graft copolymers of polyacrylamide and poly(propylene oxide) were synthesized by a micellar copolymerization technique. The rheological properties of the copolymers solutions were evaluated and compared with literature data for solutions of the same copolymers, synthesized by solution polymerization. The effect of hydrophobe content, salt addition and surfactant addition on the rheological properties were also investigated. Increasing hydrophobe content resulted in higher solution viscosities in the semi-dilute regime. Upon addition of salts, the hydrophobic groups associated to minimize their exposure to water. In the semi-dilute region, higher contents of surfactant added resulted in lower reduced viscosities of the polymer solutions. The copolymers were qualitatively characterized by infra-red spectrometry. (author)

Reaction mechanisms in the radiolysis of peptides, polypeptides and proteins

International Nuclear Information System (INIS)

Garrison, W.M.

1985-01-01

The purpose of this review is to bring together and to correlate the wide variety of experimental studies that provide information on the reaction products and reaction mechanisms involved in the radiolysis of peptides, polypeptides and proteins (including chromosomal proteins) in both aqueous and solid-state systems. The comparative radiation chemistry of these systems is developed in terms of specific reactions of the peptide main-chain and the aliphatic, aromatic-unsaturated and sulfur-containing side-chains. Information obtained with the various experimental techniques of product analysis, competition kinetics, spin-trapping, pulse radiolysis and ESR spectroscopy is included. 147 refs

Reaction mechanisms in the radiolysis of peptides, polypeptides and proteins

Energy Technology Data Exchange (ETDEWEB)

Garrison, W.M.

1985-01-01

The purpose of this review is to bring together and to correlate the wide variety of experimental studies that provide information on the reaction products and reaction mechanisms involved in the radiolysis of peptides, polypeptides and proteins (including chromosomal proteins) in both aqueous and solid-state systems. The comparative radiation chemistry of these systems is developed in terms of specific reactions of the peptide main-chain and the aliphatic, aromatic-unsaturated and sulfur-containing side-chains. Information obtained with the various experimental techniques of product analysis, competition kinetics, spin-trapping, pulse radiolysis and ESR spectroscopy is included. 147 refs.

Reaction list for charged-particle-induced nuclear reactions: Z = 1 to Z = 98 (H to Cf), July 1973--September 1974

International Nuclear Information System (INIS)

McGowan, F.K.; Milner, W.T.

1975-01-01

This Reaction List for charged-particle-induced nuclear reactions has been prepared from the journal literature for the period from July 1973 through September 1974. Each published experimental paper is listed under the target nucleus in the nuclear reaction with a brief statement of the type of data in the paper. The nuclear reaction is denoted by A(a,b)B, where the mass of a is greater than or equal to (one nucleon mass). There is no restriction on energy. Nuclear reactions involving mesons in the outgoing channel are not included. Theoretical papers which treat directly with the analysis of nuclear reaction data and results are included in the Reaction List. The cutoff date for literature was September 30, 1974. (U.S.)

Experimental study of the low-lying structure of 94Zr with the (n,n'γ) reaction

International Nuclear Information System (INIS)

Elhami, E.; Orce, J. N.; Scheck, M.; Mukhopadhyay, S.; Choudry, S. N.; McEllistrem, M. T.; Yates, S. W.; Angell, C.; Boswell, M.; Karwowski, H. J.; Fallin, B.; Howell, C. R.; Hutcheson, A.; Parpottas, Y.; Tonchev, A. P.; Tornow, W.; Kelley, J. H.

2008-01-01

The low-lying structure of 40 94 Zr was studied with the (n,n ' γ) reaction, and a level scheme was established based on excitation function and γγ coincidence measurements. Branching ratios, multipole mixing ratios, and spin assignments were determined from angular distribution measurements. Lifetimes of levels up to 3.4 MeV were measured by the Doppler-shift attenuation method, and for many transitions the reduced transition probabilities were determined. In addition to the anomalous 2 2 + state, which has a larger B(E2;2 2 + →0 1 + ) value than the B(E2;2 1 + →0 1 + ), the experimental results revealed interesting and unusual properties of the low-lying states in 94 Zr. In a simple interpretation, the excited states are classified in two distinct categories, i.e., those populating the 2 2 + state and those decaying to the 2 1 + state

Controlled release of diclofenac sodium from pH-responsive ...

Indian Academy of Sciences (India)

Administrator

copolymerization of acrylic acid (AA) onto kappa-carrageenan, using ammonium persulfate ... troscopy was carried out to confirm the chemical structure of the hydrogel. ... of hydrogel systems and influence of pH of the ... Finally, the gel product was poured into 100 mL of ... chemical reaction during the matrix formation.

Heterogeneous reaction mechanisms and kinetics relevant to the CVD of semiconductor materials

Energy Technology Data Exchange (ETDEWEB)

Creighton, J.R.; Coltrin, M.E.

1994-03-01

This report documents the state of the art in experimental and theoretical techniques for determining reaction mechanisms and chemical kinetics of heterogeneous reactions relevant to the chemical vapor deposition of semiconductor materials. It summarizes the most common ultra-high vacuum experimental techniques that are used and the types of rate information available from each. Several case studies of specific chemical systems relevant to the microelectronics industry are described. Theoretical methods for calculating heterogeneous reaction rate constants are also summarized.

Experimental effects of dynamics and thermodynamics in nuclear reactions on the symmetry energy as seen by the CHIMERA 4 π detector

Energy Technology Data Exchange (ETDEWEB)

De Filippo, E.; Pagano, A. [INFN, Catania (Italy)

2014-02-15

Heavy-ion collisions have been widely used in the last decade to constrain the parameterizations of the symmetry energy term of the nuclear equation of state (EOS) for asymmetric nuclear matter as a function of baryonic density. In the Fermi energy domain one is faced with variations of the density within a narrow range of values around the saturation density ρ{sub 0}=0.16 fm{sup -3} down towards sub-saturation densities. The experimental observables which are sensitive to the symmetry energy are constructed starting from the detected light particles, clusters and heavy fragments that, in heavy-ion collisions, are generally produced by different emission mechanisms at different stages and time scales of the reaction. In this review the effects of dynamics and thermodynamics on the symmetry energy in nuclear reactions are discussed and characterized using an overview of the data taken so far with the CHIMERA multi detector array. (orig.)

Computer aided design, analysis and experimental investigation of membrane assisted batch reaction-separation systems

DEFF Research Database (Denmark)

Mitkowski, Piotr Tomasz; Buchaly, Carsten; Kreis, Peter

2009-01-01

Membrane assisted batch reaction operation offers an interesting option for equilibrium limited reaction systems in chemical and biochemical manufacturing by selective removal of one of the products and thereby increasing the product yield. The design of such hybrid systems need to take into acco......Membrane assisted batch reaction operation offers an interesting option for equilibrium limited reaction systems in chemical and biochemical manufacturing by selective removal of one of the products and thereby increasing the product yield. The design of such hybrid systems need to take...... into account the performance of each constituent element and the optimisation of the design must take into consideration their interdependency. In this paper use of a membrane, to assist in the synthesis of propyl-propionate is investigated through the use of a hybrid process design framework, which consists...... and separation functionalities and to design/analyse the hybrid scheme. The generated hybrid scheme has been validated through experiments involving an esterification reaction....

Computational and Experimental Study of Thermodynamics of the Reaction of Titania and Water at High Temperatures.

Science.gov (United States)

Nguyen, Q N; Bauschlicher, C W; Myers, D L; Jacobson, N S; Opila, E J

2017-12-14

Gaseous titanium hydroxide and oxyhydroxide species were studied with quantum chemical methods. The results are used in conjunction with an experimental transpiration study of titanium dioxide (TiO 2 ) in water vapor-containing environments at elevated temperatures to provide a thermodynamic description of the Ti(OH) 4 (g) and TiO(OH) 2 (g) species. The geometry and harmonic vibrational frequencies of these species were computed using the coupled-cluster singles and doubles method with a perturbative correction for connected triple substitutions [CCSD(T)]. For the OH bending and rotation, the B3LYP density functional theory was used to compute corrections to the harmonic approximations. These results were combined to determine the enthalpy of formation. Experimentally, the transpiration method was used with water contents from 0 to 76 mol % in oxygen or argon carrier gases for 20-250 h exposure times at 1473-1673 K. Results indicate that oxygen is not a key contributor to volatilization, and the primary reaction for volatilization in this temperature range is TiO 2 (s) + H 2 O(g) = TiO(OH) 2 (g). Data were analyzed with both the second and third law methods using the thermal functions derived from the theoretical calculations. The third law enthalpy of formation at 298.15 K for TiO(OH) 2 (g) at 298 K was -838.9 ± 6.5 kJ/mol, which compares favorably to the theoretical calculation of -838.7 ± 25 kJ/mol. We recommend the experimentally derived third law enthalpy of formation at 298.15 K for TiO(OH) 2 , the computed entropy of 320.67 J/mol·K, and the computed heat capacity [149.192 + (-0.02539)T + (8.28697 × 10 -6 )T 2 + (-15614.05)/T + (-5.2182 × 10 -11 )/T 2 ] J/mol-K, where T is the temperature in K.

Thermally-induced amphibole reaction rim development: EBSD insights into microlite orientation

Science.gov (United States)

De Angelis, Sarah; Lavallée, Yan; Larsen, Jessica; Mariani, Elisabetta

2014-05-01

Amphibole is an important mineral present in many calc-alkaline volcanic deposits. A hydrous phase, volcanic amphibole is only stable at pressures greater than 100 MPa (approx. 4 km), temperature less than ~860-870 oC, and in melts containing at least 4 wt % H2O. When removed from their thermal and barometric stability field, amphiboles decompose to form aggregate rims of anhydrous minerals. The thickness, texture, and mineralogy of these rims are thought to be reflective of the process driving amphibole disequilibrium (e.g. heating, decompression, etc). However, significant overlap in rim thicknesses and microlite textures means that distinguishing between processes it not simple. This study employed backscatter diffraction (EBSD) to examine both experimental heating-indced amphibole reaction rims and natural amphibole reaction rim from Augustine Volcano. We collected crystal orientation maps of amphibole reaction rims to investigate if different types of disequilibrium produce different patterns of microlite orientation. We identified two types of reaction rim: Type 1- reaction rim microlites are generally oriented at random and share little or no systematic relationship with the crystallographic orientation of the host amphibole, and; Type 2- reaction rim microlites exhibit a topotactic relationship with the host amphibole (they share the same crystallographic orientation). Experimentally produced heating reaction rims are without exception Type 2. However the natural reaction rims are evenly distributed between Types 1 and 2. Further experimental data on decompression induced reaction rim formation is needed to investigate if Type 1 reaction rims resemble the breakdown of amphibole due to decompression. If so, reaction rim microlite orientation could provide a clear method for distinguishing between heating and decompression processes in amphibole bearing magmas.

Phthalimide containing donor-acceptor polymers for effective dispersion of single-walled carbon nanotubes

Directory of Open Access Journals (Sweden)

Baris Yilmaz

2015-08-01

Full Text Available Single-walled carbon nanotubes have been dispersed by novel phthalimide containing donor-acceptor type copolymers in organic media. Brominated phthalimide comonomer has been copolymerized with several electron rich structures using Suzuki and Stille coupling reactions. Carbon nanotube dispersion capability of the resultant polymers has been assessed by exploiting the non-covalent interaction of nanotube surface with the pi-system of conjugated backbone of polymers. Four polymers have been found to be good candidates for individually dispersing nanotubes in solution. In order to identify the dispersed nanotube species, 2D excitation-emission map and Raman spectroscopy have been performed. Molecular dynamics modelling has been utilized to reveal the binding energies of dispersants with the nanotube surface and the simulation results have been compared with the experimental findings. Both experimental and theoretical results imply the presence of a complex mechanism that governs the extent of dispersion capacity and selectivity of each conjugated polymeric dispersant in solubilizing carbon nanotubes.

Catalytic Upgrading of Biomass-Derived Compounds via C-C Coupling Reactions. Computational and Experimental Studies of Acetaldehyde and Furan Reactions in HZSM-5

Energy Technology Data Exchange (ETDEWEB)

Liu, Cong [Argonne National Lab. (ANL), Argonne, IL (United States); Evans, Tabitha J. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Cheng, Lei [Argonne National Lab. (ANL), Argonne, IL (United States); Nimlos, Mark R. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Mukarakate, Calvin [National Renewable Energy Lab. (NREL), Golden, CO (United States); Robichaud, David J. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Assary, Rajeev S. [Argonne National Lab. (ANL), Argonne, IL (United States); Curtiss, Larry A. [Argonne National Lab. (ANL), Argonne, IL (United States)

2015-10-02

These catalytic C–C coupling and deoxygenation reactions are essential for upgrading of biomass-derived oxygenates to fuel-range hydrocarbons. Detailed understanding of mechanistic and energetic aspects of these reactions is crucial to enabling and improving the catalytic upgrading of small oxygenates to useful chemicals and fuels. Using periodic density functional theory (DFT) calculations, we have investigated the reactions of furan and acetaldehyde in an HZSM-5 zeolite catalyst, a representative system associated with the catalytic upgrading of pyrolysis vapors. Comprehensive energy profiles were computed for self-reactions (i.e., acetaldehyde coupling and furan coupling) and cross-reactions (i.e., acetaldehyde + furan) of this representative mixture. Major products proposed from the computations are further confirmed using temperature controlled mass spectra measurements. Moreover, the computational results show that furan interacts with acetaldehyde in HZSM-5 via an alkylation mechanism, which is more favorable than the self-reactions, indicating that mixing furans with aldehydes could be a promising approach to maximize effective C–C coupling and dehydration while reducing the catalyst deactivation (e.g., coke formation) from aldehyde condensation.

Rates of the main thermonuclear reactions

International Nuclear Information System (INIS)

Abramovich, S.N.; Guzhovskii, B.Ya.; Dunaeva, S.A.; Fomushkin, E.F.

1992-01-01

The data on the cross sections of main thermonuclear reactions have been estimated with an account of the latest experimental results in a form of S-factor spline presentation. Based on this estimation, the reates of these reactions in 0.0001-1 MeV temperature range in the supposition of Maxwell distribution of relative velocities have been computed. The Maxwell-Boltzmann averaged -factors were calculated according to the table values of the reaction rates. Then the -factors were approximated with the 3 order spline-function. The necessity of the account of electron shielding and intramolecular movement at low temperatures is discussed (orig.)

Preparation of hydrophilic and antifouling polysulfone ultrafiltration membrane derived from phenolphthalin by copolymerization method

International Nuclear Information System (INIS)

Liu, Zhixiao; Mi, Zhiming; Chen, Chunhai; Zhou, Hongwei; Zhao, Xiaogang; Wang, Daming

2017-01-01

Graphical abstract: The mechanisms fouling and cleaning process of PSF-COOH membranes (A) the content of carboxyl less than 80%. (B) the content of carboxyl at 80%, 100%. - Highlights: • Phenolphthalin (PPL) containing carboxyl was successfully introduced into the molecule backbone of polysulfone (PSF). • A series of PSF-COOH copolymers with different carboxylation degree was synthesized and prepared as ultrafiltration membranes. • The introduction of PPL significantly improved the hydrophilicity, permeation flux and antifouling property of membranes. • This method is valuable for large-scale industrial production of hydrophilic membrane material. - Abstract: In this task, carboxylated polysulfone (PSF-COOH) was achieved by introducing the monomer of phenolphthalin (PPL) containing carboxyl to the molecule backbone of polysulfone (PSF). And a series of PSF-COOH copolymers with different carboxylation degree was synthesized by adjusting the molar (%) of bisphenol A (BPA) and PPL in direct copolymerization method and was prepared as PSF-COOH ultrafiltration membranes via phase separation method. The effect of PPL molar (%) in copolymers on the morphology, hydrophilicity, permeation flux, antifouling and mechanical properties of membranes was investigated by scanning electron microscope (SEM), atomic force microscope (AFM), water contact angle, ultrafiltration experiments and universal testing machine, respectively. The results showed that with the increased carboxyl content in membranes, the hydrophilicity, permeation fluxes and antifouling properties of membranes gradually increased. When the molar (%) of PPL to BPA was 100:0, the membrane exhibited the highest pure water flux (329.6 L/m"2 h) and the maximum flux recovery rate (92.5%). When the content of carboxyl in the membrane was 80% or more, after three cycles of BSA solution (1 g/L) filtration, the flux recovery rate was basically constant or showed a slightly increase. Thus, it can achieve the goal of

Preparation of hydrophilic and antifouling polysulfone ultrafiltration membrane derived from phenolphthalin by copolymerization method

Energy Technology Data Exchange (ETDEWEB)

Liu, Zhixiao; Mi, Zhiming; Chen, Chunhai; Zhou, Hongwei; Zhao, Xiaogang; Wang, Daming, E-mail: wangdaming@jlu.edu.cn

2017-04-15

Graphical abstract: The mechanisms fouling and cleaning process of PSF-COOH membranes (A) the content of carboxyl less than 80%. (B) the content of carboxyl at 80%, 100%. - Highlights: • Phenolphthalin (PPL) containing carboxyl was successfully introduced into the molecule backbone of polysulfone (PSF). • A series of PSF-COOH copolymers with different carboxylation degree was synthesized and prepared as ultrafiltration membranes. • The introduction of PPL significantly improved the hydrophilicity, permeation flux and antifouling property of membranes. • This method is valuable for large-scale industrial production of hydrophilic membrane material. - Abstract: In this task, carboxylated polysulfone (PSF-COOH) was achieved by introducing the monomer of phenolphthalin (PPL) containing carboxyl to the molecule backbone of polysulfone (PSF). And a series of PSF-COOH copolymers with different carboxylation degree was synthesized by adjusting the molar (%) of bisphenol A (BPA) and PPL in direct copolymerization method and was prepared as PSF-COOH ultrafiltration membranes via phase separation method. The effect of PPL molar (%) in copolymers on the morphology, hydrophilicity, permeation flux, antifouling and mechanical properties of membranes was investigated by scanning electron microscope (SEM), atomic force microscope (AFM), water contact angle, ultrafiltration experiments and universal testing machine, respectively. The results showed that with the increased carboxyl content in membranes, the hydrophilicity, permeation fluxes and antifouling properties of membranes gradually increased. When the molar (%) of PPL to BPA was 100:0, the membrane exhibited the highest pure water flux (329.6 L/m{sup 2} h) and the maximum flux recovery rate (92.5%). When the content of carboxyl in the membrane was 80% or more, after three cycles of BSA solution (1 g/L) filtration, the flux recovery rate was basically constant or showed a slightly increase. Thus, it can achieve the

Experimental study of sodium fires on concrete based on the sodium-concrete reaction and its consequences: study of the behavior of various concretes under metallic sheaths

International Nuclear Information System (INIS)

Berlin; Colome, J.; Malet, J.C.

The problem created by the violent reaction between hot sodium and concrete has only recently been recognized. Its importance was evidenced during experiments in which the sodium-barium oxide concrete reactions led to violent explosions. SESR approached this question during its experimental programs Cassandre and Lucifer. The Cassandre 01 experiment demonstrated the sodium-ordinary concrete reaction, where sodium was burned directly in a concrete vat. The consequences of this fire, pulverization of sodium particles, explosions and deterioration of the concrete led to consideration of protecting the concrete. Among possible shieldings sheath metal appeared to be the safest solution. The Cassandre 08, Lucifer 01 and Lucifer 04 experiments were used to study the behavior of various qualities of concrete protected from fire by a metal wall. The results show that a metal cladding efficiently protects concrete from sodium leaks

Isotope exchange reaction in Li2ZrO3 packed bed

International Nuclear Information System (INIS)

Kawamura, Y.; Enoeda, M.; Okuno, K.

1998-01-01

To understand the release behavior of bred tritium in a solid breeder blanket, the tritium transfer rate and tritium inventory for various mass transfer processes should be investigated. The contribution of the surface reactions (adsorption, desorption and two kinds of isotope exchange reactions) to the release process cannot be ignored. It is believed that two kinds of isotope exchange reactions (gaseous hydrogen-tritiated water and water vapor-tritiated water) occur on the surface of the solid breeder materials when hydrogen is added to the sweep gas to enhance the tritium release rate. The isotope exchange reaction study in H-D systems was carried out using a Li 2 ZrO 3 packed bed. The exchange reaction between gaseous hydrogen and water was the rate controlling step among the two kinds of exchange reactions. The reaction rate constants were quantified, and experimental equations were proposed. The equilibrium constant of the isotope exchange reaction in the H-D system was obtained from experimental data and was found to be 1.17. (orig.)

The path to improved reaction rates for astrophysics

International Nuclear Information System (INIS)

Rauscher, T.

2011-01-01

This review focuses on nuclear reactions in astrophysics and, more specifically, on reactions with light ions (nucleons and α particles) proceeding via the strong interaction. It is intended to present the basic definitions essential for studies in nuclear astrophysics, to point out the differences between nuclear reactions taking place in stars and in a terrestrial laboratory, and to illustrate some of the challenges to be faced in theoretical and experimental studies of those reactions. The discussion revolves around the relevant quantities for astrophysics, which are the astrophysical reaction rates. The sensitivity of the reaction rates to the uncertainties in the prediction of various nuclear properties is explored and some guidelines for experimentalists are also provided. (author)

Extension of the energy range of experimental activation cross-sections data of deuteron induced nuclear reactions on indium up to 50MeV.

Science.gov (United States)

Tárkányi, F; Ditrói, F; Takács, S; Hermanne, A; Ignatyuk, A V

2015-11-01

The energy range of our earlier measured activation cross-sections data of longer-lived products of deuteron induced nuclear reactions on indium were extended from 40MeV up to 50MeV. The traditional stacked foil irradiation technique and non-destructive gamma spectrometry were used. No experimental data were found in literature for this higher energy range. Experimental cross-sections for the formation of the radionuclides (113,110)Sn, (116m,115m,114m,113m,111,110g,109)In and (115)Cd are reported in the 37-50MeV energy range, for production of (110)Sn and (110g,109)In these are the first measurements ever. The experimental data were compared with the results of cross section calculations of the ALICE and EMPIRE nuclear model codes and of the TALYS 1.6 nuclear model code as listed in the on-line library TENDL-2014. Copyright © 2015 Elsevier Ltd. All rights reserved.

SYNTHESIS AND POLYMERIZATION OF α-METHACRYLYOXYL-ETHYLOXYCARBONYLMETHYL- ω-(N,N-DIETHYLDITHIOCARBAMYL) POLYSTYRENE MACROMONOMERS

Institute of Scientific and Technical Information of China (English)

Shu-hui Qin; Kun-yuan Qiu

2000-01-01

Polystyrene macromonomers with different molecular weight were prepared by radical polymerization of styrene (St) in benzene using β-methacryloxylethyl 2-N,N-diethyldithiocarbamylacetate (MAEDCA) as a monomer-iniferter.Characterization of the macromonomer by 1H-NMR showed that the end groups were α-methacrylyoxylethyloxycarbonyl-methyl and ω-(N,N-diethyldithiocarbamyl). The macromonomer was difficult to homopolymerize, but it was easily copolymerized with methyl methacrylate (MMA) initiated by AIBN to form graft copolymers (PMMA-g-PSt) with PSt branches randomly distributed along the PMMA backbone. Copolymerization reaction and the structure of the graft copolymers were strongly affected by Mn and concentration of the macromonomer. The composition and Mn of the purified graft copolymer were determined by 1H-NMR and GPC analysis.

Radiation-sensitive diacrylates

International Nuclear Information System (INIS)

Demajistre, R.

1976-01-01

Novel diacrylates are prepared by reacting a monohydroxylated acrylic monomer with a polyisocyanate. The reaction product may be polymerized by subjecting to ionizing irradiation, actinic light or to free radical catalysts to form a useful coating material. The diacrylates may also be copolymerized with other radiation sensitive materials. 6 claims, no drawings

Development of sodium alginate and konkoli gumgrafted ...

African Journals Online (AJOL)

This experiment is a continuation of our effort to develop a blend membrane of sodium alginate and “konkoli” gum-g-polyacrylamide (KG-g-PAAm) for bioremediation of wastewater. The effect of graft reaction conditions on the percentage graft yield in the graft copolymerization was investigated. It was observed that grafting ...

Combined experimental and theoretical approach to understand the reactivity of a mononuclear Cu(II)-hydroperoxo complex in oxygenation reactions.

Science.gov (United States)

Kamachi, Takashi; Lee, Yong-Min; Nishimi, Tomonori; Cho, Jaeheung; Yoshizawa, Kazunari; Nam, Wonwoo

2008-12-18

A copper(II) complex bearing a pentadentate ligand, [Cu(II)(N4Py)(CF(3)SO(3))(2)] (1) (N4Py = N,N-bis(2-pyridylmethyl)bis(2-pyridyl)methylamine), was synthesized and characterized with various spectroscopic techniques and X-ray crystallography. A mononuclear Cu(II)-hydroperoxo complex, [Cu(II)(N4Py)(OOH)](+) (2), was then generated in the reaction of 1 and H(2)O(2) in the presence of base, and the reactivity of the intermediate was investigated in the oxidation of various substrates at -40 degrees C. In the reactivity studies, 2 showed a low oxidizing power such that 2 reacted only with triethylphosphine but not with other substrates such as thioanisole, benzyl alcohol, 1,4-cyclohexadiene, cyclohexene, and cyclohexane. In theoretical work, we have conducted density functional theory (DFT) calculations on the epoxidation of ethylene by 2 and a [Cu(III)(N4Py)(O)](+) intermediate (3) at the B3LYP level. The activation barrier is calculated to be 39.7 and 26.3 kcal/mol for distal and proximal oxygen attacks by 2, respectively. This result indicates that the direct ethylene epoxidation by 2 is not a plausible pathway, as we have observed in the experimental work. In contrast, the ethylene epoxidation by 3 is a downhill and low-barrier process. We also found that 2 cannot be a precursor to 3, since the homolytic cleavage of the O-O bond of 2 is very endothermic (i.e., 42 kcal/mol). On the basis of the experimental and theoretical results, we conclude that a mononuclear Cu(II)-hydroperoxo species bearing a pentadentate N5 ligand is a sluggish oxidant in oxygenation reactions.

Study of the reaction of astrophysical interest 60Fe(n,γ)61Fe via (d,pγ) transfer reaction

International Nuclear Information System (INIS)

Giron, S.

2011-12-01

60 Fe is of special interest in nuclear astrophysics. Indeed the recent observations of 60 Fe characteristic gamma-ray lines by the RHESSI and INTEGRAL spacecrafts allowed to measure the total flux of 60 Fe over the Galaxy. Moreover the observation in presolar grains of an excess of the daughter-nuclei of 60 Fe, 60 Ni, gives constraints on the conditions of formation of the early solar system. However, the cross-sections of some reactions involved in 60 Fe nucleosynthesis and included to stellar models are still uncertain. The destruction reaction of 60 Fe, 60 Fe(n, γ) 61 Fe, is one of them. The total cross-section can be separate into two contributions: the direct one, involving states below the neutron separation threshold of 61 Fe, and the resonant one.We improved 61 Fe spectroscopy in order to evaluate the direct capture part of the 60 Fe(n, γ) 61 Fe reaction cross-section. 60 Fe(n, γ) 61 Fe was thus studied via d( 60 Fe, pγ) 61 Fe transfer reaction with the CATS/MUST2/EXOGAM setup at LISE-GANIL. DWBA analysis of experimental proton differential cross-sections allowed to extract orbital angular momentum and spectroscopic factors of different populated states identified below the neutron threshold. A comparison of experimental results for 61 Fe with experimental results for similar nuclei and with shell-model calculations was also performed. (author) [fr

Experimental Observation of Nuclear Reactions in Palladium and Uranium - Possible Explanation by Hydrex Mode

International Nuclear Information System (INIS)

Dufour, J.; Murat, D.; Dufour, X.; Foos, J.

2001-01-01

Experiments with uranium are presented that show a highly exothermal reaction, which can only be of nuclear origin. One striking point of these results is that they clearly show that what is being observed is not some kind of fusion reaction of the deuterium present (only exceedingly small amounts of it are present). This is a strong indication that hydrogen can trigger nuclear reactions that seem to involve the nuclei of the lattice (which would yield a fission-like pattern of products). Confronted with a situation where some experiments in the field yield a fusion-like pattern of products (CF experiments) and others a fissionlike one (LENR experiments), one can reasonably wonder whether one is not observing two aspects of the same phenomenon. Thus, it is proposed to describe CF and LENR reactions as essentially the same phenomenon based on the possible existence of a still hypothetical proton/electron resonance, which would catalyze fissionlike reactions with a neutron sink. Finally, a series of experiments is proposed to assess this hypothesis

Nuclear alignment following compound nucleus reactions

International Nuclear Information System (INIS)

Butler, P.A.; Nolan, P.J.

1981-01-01

A procedure for calculating the alignment of a nuclear state populated by a compound nucleus reaction is given and used to investigate how alignment varies for different types of population mechanisms. The calculations are compared to both predictions of Gaussian models for the state population distribution and to experimental data, for a variety of types of nuclear reactions. The treatment of alignment in the analysis of γ-ray angular distribution is discussed. (orig.)

Asian collaboration on nuclear reaction data compilation

International Nuclear Information System (INIS)

Aikawa, Masayuki; Furutachi, Naoya; Kato, Kiyoshi; Makinaga, Ayano; Devi, Vidya; Ichinkhorloo, Dagvadorj; Odsuren, Myagmarjav; Tsubakihara, Kohsuke; Katayama, Toshiyuki; Otuka, Naohiko

2013-01-01

Nuclear reaction data are essential for research and development in nuclear engineering, radiation therapy, nuclear physics and astrophysics. Experimental data must be compiled in a database and be accessible to nuclear data users. One of the nuclear reaction databases is the EXFOR database maintained by the International Network of Nuclear Reaction Data Centres (NRDC) under the auspices of the International Atomic Energy Agency. Recently, collaboration among the Asian NRDC members is being further developed under the support of the Asia-Africa Science Platform Program of the Japan Society for the Promotion of Science. We report the activity for three years to develop the Asian collaboration on nuclear reaction data compilation. (author)

Department of Nuclear Reactions: Overview

International Nuclear Information System (INIS)