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  • 101.
    Farzaneh, Amirfarrokh
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Richards, Tobias
    University of Borås.
    Heiningen, Adrian van
    Aalto University, Espoo.
    Sklavounos, Evangelos
    Aalto University, Espoo.
    A Kinetic Study of CO2 and Steam Gasification of Char from Lignin Produced in the SEW Process2014Inngår i: BioResources, ISSN 1930-2126, E-ISSN 1930-2126, Vol. 9, nr 2, s. 3052-3063Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    The reaction kinetics of gasification are important for the design of gasifiers using biomass feedstocks, such as lignin, produced in biorefinery processes. Condensed and uncondensed lignin samples used in the present study were prepared using the SEW (SO2-ethanol-water) fractionation process applied to spruce wood chips: the dissolved lignin is precipitated during the recovery of SO2 and ethanol from the spent fractionation liquor. The gasification of char made from condensed and uncondensed SEW lignin was investigated using thermogravimetric analysis (TGA) at atmospheric pressure using either CO2 or steam. The main aim of this study was to quantify the reaction rate during the gasification process, which was found to be best described as zero-order. All experiments were performed at constant temperatures between 700 and 1050 °C to obtain the necessary information for describing the reaction rate equation in an Arrhenius form; the heating rate was 20 °C/min for both samples. The experiments led to almost similar results for both samples. The activation energies of CO2 gasification were approximately 160 kJ/mol and 170 kJ/mol for uncondensed and condensed lignin char, respectively. The activation energies of steam gasification were approximately 90 kJ/mol and 100 kJ/mol for uncondensed and condensed lignin char, respectively.

  • 102.
    Farzaneh, Amirfarrokh
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Zhou, Ming
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Antzutkin, Oleg
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Bacsik, Zoltan
    Department of Materials and Environmental Chemistry, Stockholm University.
    Hedlund, Jonas
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Holmgren, Allan
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Grahn, Mattias
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Adsorption of Butanol and Water Vapors in Silicalite‑1 Films with a Low Defect Density2016Inngår i: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 32, s. 11789-11798Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Pure silica zeolites are potentially hydrophobic and have therefore been considered to be interesting candidates for separating alcohols, e.g., 1-butanol, from water. Zeolites are traditionally synthesized at high pH, leading to the formation of intracrystalline defects in the form of silanol defects in the framework. These silanol groups introduce polar adsorption sites into the framework, potentially reducing the adsorption selectivity toward alcohols in alcohol/water mixtures. In contrast, zeolites prepared at neutral pH using the fluoride route contain significantly fewer defects. Such crystals should show a much higher butanol/water selectivity than crystals prepared in traditional hydroxide (OH−) media. Moreover, silanol groups are present at the external surface of the zeolite crystals; therefore, minimizing the external surface of the studied adsorbent is important. In this work, we determine adsorption isotherms of 1-butanol and water in silicalite-1 films prepared in a fluoride (F−) medium using in situ attenuated total reflectance−Fourier transform infrared (ATR−FTIR) spectroscopy. This film was composed of well intergrown, plate-shaped b-oriented crystals, resulting in a low external area. Single-component adsorption isotherms of 1-butanol and water were determined in the temperature range of 35− 80 °C. The 1-butanol isotherms were typical for an adsorbate showing a high affinity for a microporous material and a large increase in the amount adsorbed at low partial pressures of 1-butanol. The Langmuir−Freundlich model was successfully fitted to the 1-butanol isotherms, and the heat of adsorption was determined. Water showed a very low affinity for the adsorbent, and the amounts adsorbed were very similar to previous reports for large silicalite-1 crystals prepared in a fluoride medium. The sample also adsorbed much less water than did a reference silicalite-1(OH−) film containing a high density of internal defects.The results show that silicalite-1 films prepared in a F− medium with a low density of defects and external area are very promising for the selective recovery of 1-butanol from aqueous solutions.

  • 103.
    Farzaneh, Amirfarrokh
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Zhou, Ming
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Potapova, Elisaveta
    Bacsik, Zoltan
    Department of Materials and Environmental Chemistry, Stockholm University.
    Ohlin, Lindsay
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Holmgren, Allan
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Hedlund, Jonas
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Grahn, Mattias
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Adsorption of Water and Butanol in Silicalite-1 Film Studied with in-situ ATR-FTIR Spectroscopy2015Inngår i: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 31, nr 17, s. 4887-4894Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Biobutanol produced by, e.g., acetone–butanol–ethanol (ABE) fermentation is a promising alternative to petroleum-based chemicals as, e.g., solvent and fuel. Recovery of butanol from dilute fermentation broths by hydrophobic membranes and adsorbents has been identified as a promising route. In this work, the adsorption of water and butanol vapor in a silicalite-1 film was studied using in situ attenuated total reflectance–Fourier transform infrared (ATR–FTIR) spectroscopy to better understand the adsorption properties of silicalite-1 membranes and adsorbents. Single-component adsorption isotherms were determined in the temperature range of 35–120 °C, and the Langmuir model was successfully fitted to the experimental data. The adsorption of butanol is very favorable compared to that of water. When the silicalite-1 film was exposed to a butanol/water vapor mixture with 15 mol % butanol (which is the vapor composition of an aqueous solution containing 2 wt % butanol, a typical concentration in an ABE fermentation broth, i.e., the composition of the gas obtained from gas stripping of an ABE broth) at 35 °C, the adsorption selectivity toward butanol was as high as 107. These results confirm that silicalite-1 quite selectively adsorbs hydrocarbons from vapor mixtures. To the best of our knowledge, this is the first comprehensive study on the adsorption of water and butanol in silicalite-1 from vapor phase.

  • 104.
    Fatima, Nowshir
    et al.
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Maskinelement.
    Holmgren, Allan
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Marklund, Pär
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Maskinelement.
    Minami, Ichiro
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Maskinelement.
    Larsson, Roland
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Maskinelement.
    Degradation Mechanism of Automatic Transmission Fluid by Water as a Contaminant2015Inngår i: Proceedings of the Institution of mechanical engineers. Part J, journal of engineering tribology, ISSN 1350-6501, E-ISSN 2041-305X, Vol. 229, nr 1, s. 74-85Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    The degradation mechanism of water contaminated Automatic Transmission Fluids (ATF) was experimentally investigated. Water contaminated ATF was tribotested in a full-scale wet clutch test rig to monitor the friction durability during clutch ageing, and was also statically aged in oven to evaluate the interaction of ATF with water. The bulk properties and chemical nature of the ATF were analysed using viscosity measurements, Fourier Transform Infrared Spectroscopy (FTIR) and Thermogravimetric Analysis (TGA). It was shown that water presence in the ATF can increase the mean friction coefficient over a short time period, though in the long term perspective there is a higher loss of mean friction. Phase separation of the water-in-oil emulsion by centrifugation at 20000 rpm made it possible to examine the water phase using infrared 2spectroscopy. The spectroscopic analysis revealed the hydrophilic nature of certain ATF constituents, although the impact of water on the bulk properties like lubricant viscosity and thermal stability was insignificant. The analysis of the tribotests showed that the friction increase for water contamination was a short-term effect and likely due to the interaction between polar surface active additives and water. Even though no significant change has been found for thermal degradation or in bulk properties of the lubricant, the initially changed action of the water soluble additives and generation of high friction resulted in a total deterioration of the clutch performance during long term use.

  • 105. Fatima, Nowshir
    et al.
    Minami, Ichiro
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Maskinelement.
    Holmgren, Allan
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Marklund, Pär
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Maskinelement.
    Berglund, Kim
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Maskinelement.
    Larsson, Roland
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Maskinelement.
    Influence of water on the tribological properties of zinc dialkyl-dithiophosphate and over-based calcium sulfonate additives in wet clutch contacts2015Inngår i: Tribology International, ISSN 0301-679X, E-ISSN 1879-2464, Vol. 87, s. 113-120Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Usually the wet clutch lubricant properties vary with different formulations of base oil types and additives. The aim of this paper was to evaluate the effect of water on the performance of additives in ATF. Simplified lubricants, ZDDP and over-based Ca-sulfonates detergent additives in an API Group I mineral base oil, were employed to compare with the commercial fully-formulated automatic transmission fluid (DEXRON®VI) during water-contamination. A full-scale wet clutch test rig was used to evaluate the frictional response due to water contamination of the lubricants. Fourier Transform Infrared Spectroscopy was utilized to evaluate the variation in the solubility of these polar organic additives in the water phase and Karl-Fischer titration was utilized to evaluate the post-test water content for different formulations.

  • 106.
    Fatima, Nowshir
    et al.
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Maskinelement.
    Minami, Ichiro
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Maskinelement.
    Holmgren, Allan
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Marklund, Pär
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Maskinelement.
    Larsson, Roland
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Maskinelement.
    Adsorption of ATF additives on wet clutch friction interfaces under water contaminated lubricant conditions2014Konferansepaper (Fagfellevurdert)
    Abstract [en]

    Stable friction and positive slope of friction-speed is the typical criterion for a good clutch performance. Lubricated friction interfaces used for wet clutches produces different friction behavior depending on the lubricant conditions. Usually the lubricant conditions vary for different automatic transmission fluid (ATF) formulations implying e.g. water contamination and these conditions might influence the deterioration of the clutch plates. The aim of this paper is to verify additive adsorption on friction interfaces and ageing of the friction material in wet clutch system for a water contaminated commercial ATF (DEXRON® VI). Standard clutch plates are employed in an automated wet clutch test rig to evaluate the friction characteristics of the tested lubricant. For controlled test conditions (speed, contact pressure, oil temperature) and specific number of test cycles, the mean friction coefficient and the friction vs. speed relations are monitored during sliding test. The resultant tribofilms on the tested friction interface surfaces are characterized by means of Scanning Electron Microscopy-Energy Dispersive X-ray spectroscopy (SEM- EDS), Attenuated Total Reflectance -Fourier Transform Infrared Spectroscopy (ATR-FTIR) and X-ray Photoelectron Spectroscopy (XPS analysis). The spectroscopic techniques were used to analyse adsorbed additives on friction interfaces and made it possible to correlate measured data to the specific friction behavior obtained after water contamination of the ATF.

  • 107.
    Fatima, Nowshir
    et al.
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Maskinelement.
    Minami, Ichiro
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Maskinelement.
    Holmgren, Allan
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Marklund, Pär
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Maskinelement.
    Larsson, Roland
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Maskinelement.
    Adsorption of ATF additives on wet clutch friction interfaces under water contaminated lubricant conditions2014Konferansepaper (Fagfellevurdert)
    Abstract [en]

    Stable friction and positive slope of friction-speed is the typical criterion for a good clutch performance. Lubricated friction interfaces used for wet clutches produces different friction behavior depending on the lubricant conditions. Usually the lubricant conditions vary for different automatic transmission fluid (ATF) formulations implying e.g. water contamination and these conditions might influence the deterioration of the clutch plates. The aim of this paper is to verify additive adsorption on friction interfaces and ageing of the friction material in wet clutch system for a water contaminated commercial ATF (DEXRON® VI). Standard clutch plates are employed in an automated wet clutch test rig to evaluate the friction characteristics of the tested lubricant. For controlled test conditions (speed, contact pressure, oil temperature) and specific number of test cycles, the mean friction coefficient and the friction vs. speed relations are monitored during sliding test. The resultant tribofilms on the tested friction interface surfaces are characterized by means of Scanning Electron Microscopy-Energy Dispersive X-ray spectroscopy (SEM- EDS), Attenuated Total Reflectance -Fourier Transform Infrared Spectroscopy (ATR-FTIR) and X-ray Photoelectron Spectroscopy (XPS analysis). The spectroscopic techniques were used to analyse adsorbed additives on friction interfaces and made it possible to correlate measured data to the specific friction behavior obtained after water contamination of the ATF.

  • 108. Fatima, Nowshir
    et al.
    Minami, Ichiro
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Maskinelement.
    Holmgren, Allan
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Marklund, Pär
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Maskinelement.
    Larsson, Roland
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Maskinelement.
    Surface chemistry of wet clutch influenced by water contamination in automatic transmission fluids2016Inngår i: Tribology International, ISSN 0301-679X, E-ISSN 1879-2464, Vol. 96, s. 395-401Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Lubricated friction interfaces used for wet clutches produces different friction behaviour depending on the lubricant conditions. Usually the lubricant conditions vary for water contamination in automatic transmission fluid (ATF). The presence of water retards the ATF performance by increasing the friction and can influence the deterioration of the clutch plates. Water as a polar contaminant can change the absorbability of the surface active additives, which might cause the characteristic friction behaviour. The aim of this paper is to verify the surface chemistry of tribotested standard friction interfaces lubricated with water contaminated commercial ATF (DEXRON® VI). The evidences of the influence of water on ATF performances were shown by surface analyses

  • 109.
    Filippov, Andrei
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Self-Diffusion and Microstructure of Some Ionic Liquids in Bulk and in Confinement2016Doktoravhandling, med artikler (Annet vitenskapelig)
    Abstract [en]

    An ionic liquid (IL) is a salt, which usually is in the liquid state at normal temperature and pressure. The properties of ILs can be adjusted for various processes and applications by choosing different combinations of ions. Similar to other salts, ILs contain only ions with positive (cations) and negative (anions) charges in equal proportions. However, to prevent solidification, ions in ionic liquids usually contain bulky organic chemical groups, which, apart from electrostatic interactions, promote other types of interactions between ions, such as: (i) van-der-Waals interactions; (ii) hydrogen bonding; (iii) - stacking, etc., depending on the particular chemical structure of the ions. All these interactions, in combination, may lead to formation of specific microstructures in ILs, which may vary with temperature caused by changing thermal rotational and translational energies of the ions. Ions in these microstructures may have preferential orientations relative to each other, maintain anisotropic properties similar to those in liquid crystals or, in some specific cases, may even separate into microscopically organised liquid phases. Therefore, the dynamics of ILs may also be dependent on their microstructure. In many practical applications ionic liquids are placed on surfaces or in confinements. Solid surfaces introduce extra forces, which may be specific to the charge of the ions or/and to functional groups in the ILs. The geometry and interactions of ions in confinements or/and pores of materials may also disrupt specific bulk microstructures of ILs. Both confinement effects and interactions of ions with surfaces are manifested in the translational dynamics of the ions. One of the most direct and informative methods to study translational dynamics of ILs is pulse-field-gradient nuclear magnetic resonance (PFG-NMR).In this thesis the results of PFG-NMR studies on a few classes of ILs are reported: (i) the historically “standard” (since Walden’s discovery in 1914) ionic liquid, the ethylammonium nitrate (EAN) and (ii) halogen-free orthoborate-based phosphonium, imidazolium and pyrrolidinium ILs with varied structure and lengths of alkyl chains in cations, and varied structures of orthoborate anions. These ILs were studied in bulk at different temperatures, and also in confinements, such as between parallel glass and Teflon plates and in mesoporous Vycor glass. It was found that diffusion coefficients of cations and anions in EAN, phosphonium and pyrrolidinium orthoborate ILs in bulk are different, but according to the standard Stocks-Einstein model, they correspond to diffusion of ions in homogeneous liquids. A change in the chemical structure of one of the ions results in a change in both the diffusion coefficient of the oppositely charged ion and the activation energy of diffusion for both ions in an IL. Similar effects were observed from the chemical shifts and diffusion coefficients measured by NMR for imidazolium orthoborate ILs dissolved in polyethylene glycol solutions, in which imidazolium cations strongly interact with PEG molecules, further affecting the diffusion of orthoborate anions via electrostatic interactions. A liquid-liquid phase separation was suggested for a few phosphonium and pyrrolidinium bis(mandelato)borate ILs, in which a divergence of diffusion coefficients and activation energies of diffusion for cations and anions was detected at temperatures below ca 50 °C. In addition, a free-volume theory was invoked to explain the dependences of density of ILs on the alkyl chain length in cations.It was also found that for a phosphonium bis(salicylato)borate IL confined in 4 nm mesoporous Vycor glass the diffusion coefficients of ions increase by a factor of 35! This phenomenon was explained by the dynamic heterogeneity of this IL in micropores and empty voids of the Vycor glass. For EAN IL in confinements between glass and Teflon plates, the diffusion of ethylammonium cations and nitrate anions is significantly anisotropic, i.e. slower in the direction of the normal to the plates and faster along the plates compared to diffusion of the ions in bulk. A plausible explanation of this PFG NMR data is that EAN forms layers near polar and non-polar solid surfaces. A similar phenomenon, to a lesser extent, was also observed for phosphonium cations of bis(mandelato)borate, bis(salicylato)borate and bis(oxalato)borate confined between glass plates. The results of these studies may have implications in modeling tribological performance, i.e., friction and wear reduction for contact pairs of different materials lubricated by various classes of ionic liquids.

  • 110.
    Filippov, Andrei
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. Institute of Physics, Kazan Federal University, Kazan, Russia .
    Antzutkin, Oleg N.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. Department of Physics, Warwick University, Coventry, United Kingdom .
    Magnetic field effects dynamics of ethylammonium nitrate ionic liquid confined between glass plates2018Inngår i: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 20, nr 9, s. 6316-6320Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Self-diffusion and NMR relaxation of the ethylammonium (EA) cation were studied in the protic ionic liquid, ethylammonium nitrate (EAN), confined between polar glass plates separated by a few μm distance and exposed to an external magnetic field of 9.4 T. The diffusion coefficient of EA (D) and the transverse NMR relaxation rate (1/T2) of –NH3 protons were increased immediately after placing the sample in the magnetic field by factors of ∼2 and ∼22, respectively, in comparison with those of bulk EAN. Further exposure of the sample to the magnetic field led to gradual changes in D, T1 and T2 towards their bulk values with a time constant of ∼70 min. Complete “recovery” of the sample to the “accelerated” D and “shortened” T2 values occurred at longer than 24 hours after the removal of the EAN sample from the magnet. Because the observed characteristic times of the change far exceed the times of molecular processes in EAN, we suggested that this phenomenon is related to reversible phase transformations occurring in confined EAN.

  • 111.
    Filippov, Andrei
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. Kazan State Medical University, Kazan, Russia.
    Antzutkin, Oleg
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. Department of Physics, Warwick University, Coventry, UK.
    Shah, Faiz Ullah
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Rapid carbene formation increasing ion diffusivity in an imidazolium acetate ionic liquid confined between polar glass plates2019Inngår i: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 21, nr 40, s. 22531-22538Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    1-Ethyl-3-methyl-imidazolium acetate ([EMIM][OAc]) is one of the most widely used ionic liquids for various applications. This study is focussed on the chemical stability of [EMIM][OAc] on the surfaces of polar glass plates. 1H and 13C NMR spectroscopy and NMR diffusometry of [EMIM][OAc] IL confined between glass plates with a specific surface area 105–106 m−1 are thoroughly investigated. A rapid and spontaneous reaction took place on the surfaces of glass plates leading to the formation of neutral chemical moieties as evident by the appearance of new signals in the 1H NMR spectra. These new products are assigned as N-heterocyclic carbene (NHC) and acetic acid. These neutral chemical moieties have significantly increased the ion diffusivity by dissociation of the cation and the anion in [EMIM][OAc] IL. The yield and rate of formation of NHC and acetic acid are found to increase with the increasing surface area of polar glass plates and the time of contact between the IL and glass surfaces. Based on NMR spectroscopy, a dissociative reaction mechanism is proposed for the formation of free NHC in the neat [EMIM][OAc] IL.

  • 112.
    Filippov, Andrei
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. Kazan State Medical University, Kazan, Russia.
    Antzutkin, Oleg
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. Department of Physics, Warwick University, Coventry, UK.
    Shah, Faiz Ullah
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Reactivity of CO2 with aqueous choline-based ionic liquids probed by solid-state NMR spectroscopy2019Inngår i: Journal of Molecular Liquids, ISSN 0167-7322, E-ISSN 1873-3166, Vol. 286, artikkel-id 110918Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    CO2 absorption in a series of choline-based ionic liquids is investigated using solid-state 13C and 15N MAS NMR spectroscopy. Natural abundance and 13C enriched CO2 gas was purged through 50 wt% aqueous solutions of alkyldimethyl(2-hydroxyethyl)ammonium threonine, [N1,1,n,2OH][Threo], (alkyl = butyl, pentyl and hexyl) and pentyldimethyl(2-hydroxyethyl)ammonium taurine [N1,1,5,2OH][Tau]. The process of CO2 absorption results in precipitation of a solid sediment, which stays in equilibrium with the liquid phase. Upon degassing of the sample, the sediment is dissolved back into the IL-aqueous phase. Solid state 13C and 15N MAS NMR data suggest that the solid sediment is composed of neutral threonine (or taurine) in the zwitterionic forms and the liquid phase contained the products of reactions between the ionic liquids and CO2 molecules. A plausible mechanism for formation of the solid sediments and the reaction products in liquid phases is suggested.

  • 113.
    Filippov, Andrei
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. Kazan State Medical University, Kazan, Russia.
    Antzutkin, Oleg
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. Department of Physics, Warwick University, Coventry, U.K.
    Shah, Faiz Ullah
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Understanding the Interaction of Boric Acid and CO2 with Ionic Liquids in Aqueous Medium by Multinuclear NMR Spectroscopy2020Inngår i: ACS Sustainable Chemistry & Engineering, E-ISSN 2168-0485, Vol. 8, nr 1, s. 552-560Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Boric acid is known to enhance the kinetics of CO2 absorption by some active aqueous solutions. However, the mechanism of interaction of boric acid with CO2 in the presence of active molecules is not yet fully understood. In this work, the interaction and dynamics of ions in aqueous solutions of functionalized choline-based ionic liquids [N1,1,5,2OH][Threo] and [N1,1,5,2OH][Tau] in the presence of boric acid and CO2 was thoroughly investigated using a multinuclear NMR approach: 13C and 11B NMR spectroscopy, 11B NMR transverse relaxation, and 1H and 11B NMR diffusometry. 13C and 11B NMR spectroscopy revealed the formation of borate-based complexes as a result of a reaction between boric acid and the anions of the ILs at ionic liquid/boric acid molar ratios larger than ca. 0.15. The formation of these complexes and their dynamics were further investigated using 11B relaxation and 1H and 11B pulse-field-gradient (PFG) NMR. Plausible reaction mechanisms of boric acid with the anions of the ILs, formation of the borate complexes, and dissociation of these complexes facilitated by CO2 molecules are suggested.

  • 114.
    Filippov, Andrei
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Azancheev, Nail
    Institute of Physics, Kazan Federal University, Kazan, Russia.
    Gibaydullin, Amal
    Institute of Physics, Kazan Federal University, Kazan, Russia.
    Bhattacharyya, Shubhankar
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Antzutkin, Oleg N.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Shah, Faiz Ullah
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Dynamic Properties of Imidazolium Orthoborate Ionic Liquids Mixed with Polyethylene Glycol Studied by NMR Diffusometry and Impedance Spectroscopy2018Inngår i: Magnetic Resonance in Chemistry, ISSN 0749-1581, E-ISSN 1097-458X, Vol. 56, nr 2, s. 113-119Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    We used 1H pulsed field gradient (PFG) NMR to study the self-diffusion of polyethylene glycol (PEG) with average molecular mass of 200 and ions in mixtures of PEG with imidazolium bis(mandelato)borate (BMB) and imidazolium bis(oxalato)borate (BOB) ionic liquids (ILs). The ionic liquid was mixed with PEG in the concentration range of 0–100 wt%. Within the temperature range of 295 to 353 K, the diffusion coefficient of BMB is slower than that of the imidazolium cation. The diffusion coefficients of PEG, as well as the imidazolium cation and BMB anions, differ under all experimental conditions tested. This demonstrates that the IL in the mixture is present in at least a partially dissociated state. Generally, increasing the concentration of PEG leads to an increase in the diffusion coefficients of PEG and both the ions, and decreases their activation energy for diffusion. NMR chemical shift alteration analysis showed that the presence of PEG changes the chemical shifts of both ions but in different directions. Impedance spectroscopy was used to measure the ionic conductivity of the ionic liquids mixed with PEG.

  • 115.
    Filippov, Andrei
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Azancheev, Nail
    Kazan (Volga Region) Federal University, Kazan.
    Shah, Faiz Ullah
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Glavatskikh, Sergei
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Maskinelement.
    Antzutkin, Oleg
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Self-Diffusion of Phosphonium Bis(Salicylato)Borate Ionic Liquid in Pores of Vycor Porous Glass2016Inngår i: Microporous and Mesoporous Materials, ISSN 1387-1811, E-ISSN 1873-3093, Vol. 230, s. 128-134Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    1H NMR pulsed field gradient was used to study self-diffusion of a phosphonium bis(salicylato)borate ionic liquid ([P6,6,6,14][BScB]) in the pores of Vycor porous glass at 296 K. Confinement in pores increases diffusion coefficients of the ions by a factor of 35. However, some [P6,6,6,14][BScB] ions demonstrated apparent diffusion coefficients much lower than their mean values, which may be due to partially restricted diffusion of the ions. We suggest that this fraction corresponds to areas where ions are confined by pore ‘necks’ (micropores) and empty voids. Heating of the ionic liquid / Vycor system at 330 K led to a change in the diffusivity of the ions, because of their redistribution in the pores. The size of the bounded regions is on the order of 1 µm, as estimated from the dependence of the ion diffusivity on the diffusion time.

  • 116.
    Filippov, Andrei
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Azancheev, Nail
    Kazan (Volga Region) Federal University, Kazan.
    Taher, Mamoun
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Shah, Faiz Ullah
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Rabét, Pauline
    Department of Organic Chemistry, School of Chemistry, Manchester University.
    Glavatskih, Sergei
    System and Component Design, KTH, Royal Institute of Technology , Machine Design, KTH Royal Institute of Technology, SE-10044 Stockholm, Sweden, Department of Physics, Warwick University, Coventry, Department of Mechanical Construction and Production, Ghent University.
    Antzutkin, Oleg
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Self-diffusion and interactions in mixtures of imidazolium bis(mandelato)borate ionic liquids with polyethylene glycol: 1H NMR study2015Inngår i: Magnetic Resonance in Chemistry, ISSN 0749-1581, E-ISSN 1097-458X, Vol. 53, nr 7, s. 493-497Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    We used 1H nuclear magnetic resonance pulsed-field gradient to study the self-diffusion of polyethylene glycol (PEG) and ions in a mixture of PEG and imidazolium bis(mandelato)borate ionic liquids (ILs) at IL concentrations from 0 to 10 wt% and temperatures from 295 to 370 K. PEG behaves as a solvent for these ILs, allowing observation of separate lines in 1H NMR spectra assigned to the cation and anion as well as to PEG. The diffusion coefficients of PEG, as well as the imidazolium cation and bis(mandelato)borate (BMB) anion, differ under all experimental conditions tested. This demonstrates that the IL in the mixture is present in at least a partially dissociated state, while the lifetimes of the associated states of the ions and ions with PEG are less than ~30 ms. Generally, increasing the concentration of the IL leads to a decrease in the diffusion coefficients of PEG and both ions. The diffusion coefficient of the anion is less than that of the cation; the molecular mass dependence of diffusion of ions can be described by the Stokes–Einstein model. NMR chemical shift alteration analysis showed that the presence of PEG changes mainly the chemical shifts of protons belonging to imidazole ring of the cation, while chemical shifts of protons of anions and PEG remain unchanged. This demonstrated that the imidazolium cation interacts mainly with PEG, which most probably occurs through the oxygen of PEG and the imidazole ring. The BMB anion does not strongly interact with PEG, but it may be indirectly affected by PEG through interaction with the cation, which directly interacts with PEG

  • 117.
    Filippov, Andrei
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. Institute of Physics, Kazan Federal University, Russia.
    Bhattacharyya, Shubhankar
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Shah, Faiz Ullah
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    CO2 absorption and ion mobility in aqueous choline-based ionic liquids2019Inngår i: Journal of Molecular Liquids, ISSN 0167-7322, E-ISSN 1873-3166, Vol. 276, s. 748-752Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    CO2 absorption and ion mobility are investigated in a series of 50/50 wt% aqueous solutions of choline-based ionic liquids with different cations and anions: [N1,1,4,2OH][Threo], [N1,1,5,2OH][Threo], [N1,1,6,2OH][Threo], [N1,1,5,2OH][β-ala] and [N1,1,5,2OH][Tau]. The process of CO2 absorption was completed in an hour reaching maximum of absorption capacity 0.07–0.10 wt% to ionic liquid (by 0.4–0.6 molar ratios). A rapid CO2 absorption is observed by the formation of solid product as a result of reaction between CO2 molecule and the ionic liquid. Diffusion coefficients of the cation and anion in the mixture are comparable while the diffusivity of water molecules is found to be quite different from the ions. In the process of CO2 absorption, an increase in the diffusivity of ions is observed due to the precipitation of solid products and depletion of ions contents in the liquid phase of the system. 13C NMR measurements of diffusivity of CO2 enriched with 13C isotope showed that a part of the absorbed CO2 remained in the liquid phase being physically and chemically bound to ions. The ionic liquid is re-cycled by evaporating water and releasing CO2 molecules using vacuum and temperature.

  • 118.
    Filippov, Andrei
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Bulat, Munavirov
    System and Component Design, KTH Royal Institute of Technology, Stockholm, Sweden.
    Sergei, Glavatskih
    System and Component Design, KTH Royal Institute of Technology, Stockholm, Sweden. Department of Electromechanical, Systems and Metal Engineering, Ghent University, Ghent, Belgium. School of Chemistry, University of New South Wales, Sydney, Australia.
    Shah, Faiz Ullah
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Antzutkin, Oleg
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. Department of Physics, Warwick University, Coventry, United Kingdom.
    Diffusion of Ions in Phosphonium Orthoborate Ionic Liquids Studied by 1H and 11B Pulsed Field Gradient NMR2020Inngår i: Frontiers in Chemistry, E-ISSN 2296-2646, Vol. 8, artikkel-id 119Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Non-halogenated boron-based ionic liquids (ILs) composed of phosphonium cations and chelated orthoborate anions have high hydrolytic stability, low melting point and exceptional properties for various applications. This study is focused on ILs with the same type of cation, trihexyltetradecylphosphonium ([P6,6,6,14]+), and two orthoborate anions, such as bis(salicylato)borate ([BScB]−) and bis(oxalato)borate ([BOB]−). We compare the results of this study with our previous studies on ILs with bis(mandelato)borate ([BMB]−) and a variety of different cations (tetraalkylphosphonium, dialkylpyrrolidinium and dialkylimidazolium). The ion dynamics and phase behavior of these ILs is studied using 1H and 11B pulsed-field-gradient (PFG) NMR. PFG NMR is demonstrated to be a useful tool to elucidate the dynamics of ions in this class of phosphonium orthoborate ILs. In particular, the applicability of 11B PFG NMR for studying anions without 1H, such as [BOB]−, and the limitations of this technique to measure self-diffusion of ions in ILs are demonstrated and discussed in detail for the first time.

  • 119.
    Filippov, Andrei
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. Institute of Physics, Kazan Federal University.
    Gnezdilov, Oleg I.
    Institute of Physics, Kazan Federal University.
    Antzutkin, Oleg
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. Department of Physics, Warwick University, Coventry.
    Static magnetic field alters properties of confined alkylammonium nitrate ionic liquids2018Inngår i: Journal of Molecular Liquids, ISSN 0167-7322, E-ISSN 1873-3166, Vol. 268, s. 49-54Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Ethylammonium nitrate (EAN) and propylammonium nitrate (PAN) ionic liquids confined between polar glass plates and exposed to a strong magnetic field of 9.4 T demonstrate gradually slowing diffusivity, a process that can be reversed by removing the sample from the magnetic field. The process can be described well by the Avrami equation, which is typical for autocatalytic (particularly, nucleation controlled) processes. The transition can be stopped by freezing the sample. Cooling and heating investigations showed differences in the freezing and melting behavior of the sample depending on whether it had been exposed to the magnetic field. After exposure to the magnetic field, the sample demonstrated decrease in the 1H NMR signal of residual water. 1H NMR spectroscopy with presaturation demonstrates that the most probable mechanism of the decrease of the bulk water signal is adsorption of water on polar surfaces of glass plates. Generally, our findings confirm our previous suggestion that alteration of the dynamic properties of confined alkylammonium nitrate ionic liquids exposed to a magnetic field is related to the alteration of real physical-chemical phases

  • 120.
    Filippov, Andrei
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Gnezdilov, Oleg I.
    Institute of Physics, Kazan Federal University.
    Hjalmarsson, Nicklas
    Surface and Corrosion Science, KTH Royal Institute of Technology.
    Antzutkin, Oleg N.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Glavatskih, Sergei
    System and Component Design, Department of Machine Design, KTH Royal Institute of Technology.
    Furo, Istvan
    Applied Physical Chemistry, KTH Royal Institute of Technology.
    Rutland, Mark W.
    Surface and Corrosion Science, KTH Royal Institute of Technology.
    Acceleration of diffusion in ethylammonium nitrate ionic liquid confined between parallel glass plates2017Inngår i: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 19, nr 38, s. 25853-25858Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Diffusion of EAN confined between polar glass plates separated by a few micrometers is higher by a factor of ca. 2 as compared to bulk values. Formation of a new phase, different to the bulk, was suggested.

  • 121.
    Filippov, Andrei
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. Kazan State Medical University, Kazan, Russia.
    Gnezdilov, Oleg I.
    Kazan Federal University, Kazan, Russia. Zavoisky Physical-Technical Institute, FRC Kazan Scientific Center, Russian Academy of Sciences, Kazan, Russia.
    Luchkin, Alexander G.
    Kazan Federal University, Kazan, Russia.
    Antzutkin, Oleg
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Self-diffusion of ethylammonium nitrate ionic liquid confined between modified polar glasses2019Inngår i: Journal of Molecular Liquids, ISSN 0167-7322, E-ISSN 1873-3166, Vol. 284, s. 366-371Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Ethylammonium nitrate (EAN) ionic liquid confined between flat polar glass platesdemonstrates variable diffusivity that is sensitive to an external static magnetic field. Outside the magnetic field, diffusivity between the plates is higher than that in the bulk. However, after placing the system in a strong static magnetic field, the diffusivity gradually decreased. These processes occur during transformations between phases formed in EAN subjected to micrometer-size restrictions outside and within the magnetic field (Filippov et al., JMolLiq. [2018] 268, 49). In this study, we used samples of two types: (i) with roughened surface formed by treatment of the glass plates with aqueous solutions of hydrofluoric acid and (ii) with vacuum deposited TiO2 layers with a thickness of ca. 1 μm at glass-plate edges. Neither the surface modification of the glass plates, nor the TiO2 layers controlled thickness of EAN confined between glass-plates significantly changed the above-described effects, which have been observed in studies using untreated glass plates. Therefore, the range of systems with detected phase transformations in EAN and accompanying effects, such as accelerated diffusivity and change in diffusivity under the influence of a static magnetic field, was expanded to the systems with roughened surfaces and the systems with TiO2 layers controlled inter-plates distances. Results of experiments with roughened surfaces additionally suggested that the phase transformation of confined EAN in the external magnetic field is isotropic in nature rather than a phase transition from “layered to bulk” structures.

  • 122.
    Filippov, Andrei
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Khakimov, Aidar
    Kazan (Volga Region) Federal University, Kazan.
    Munavirov, Bulat
    Kazan (Volga Region) Federal University, Kazan, Institute of Physics, Kazan (Volga Region) Federal University.
    31P NMR Studies of Phospholipids2015Inngår i: Annual Reports on NMR Spectroscopy, ISSN 0066-4103, E-ISSN 2163-6052, Vol. 85, s. 27-92Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    31P nuclear magnetic resonance (NMR) can provide information on the composition of phospholipid (PL) membranes, lipid headgroup orientation relative to the bilayers normal, and the phase state of PL systems. Interaction of the membrane with ions, drugs, other small molecules and peptides may lead to lipid phase change and lamellar phase disturbances, which can also be revealed in 31P NMR spectra. Traditional 31P NMR spectroscopy has been used for years, mainly to study lipid phase state. In the last few years, however, its utility has been extended by a number of solid-state methods in field-cycling spectroscopy. Membrane mimicking systems have been complemented with bicelles, which are more convenient for studying peptide structure in lipid–peptide interactions. Another challenge is the study of ordered membrane domains (rafts) induced in the presence of cholesterol or certain proteins. As a result, recent work has refined the structure of PL headgroups and elucidated membrane responses to interactions with peptides and other molecules. Selected examples of such fascinating investigations are presented here.

  • 123.
    Filippov, Andrei
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Kotenkov, Sergey A.
    Kazan (Volga Region) Federal University, Kazan.
    Munavirov, Bulat
    Kazan (Volga Region) Federal University, Kazan.
    Antzutkin, Oleg
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Effect of Curcumin on Lateral Diffusion of Phosphatidylcholines in Saturated and Unsaturated Bilayers2014Inngår i: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 30, nr 35, s. 10686-10690Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Curcumin, a dietary polyphenol, is a natural spice with preventive and therapeutic potential for neurodegenerative diseases such as Alzheimer's and Parkinson's diseases. Curcumin possesses a spectrum of antioxidant, anti-inflammatory, anticarcinogenic, and antimutagenic properties. Because of this broad spectrum of pharmacological activity, it has been suggested that, like cholesterol, curcumin exerts its effect on a rather basic biological level, such as on lipid bilayers of biomembranes. The effect of curcumin on translational mobility of lipids in biomembranes has not yet been studied. In this work, we used 1H NMR diffusometry to explore lateral diffusion in planar-oriented bilayers of dimyristoylphosphatidylcholine (DMPC) and dioleoylphosphatidylcholine (DOPC) at curcumin concentrations of up to 40 mol % and in the temperature range of 298-333 K. The presence of curcumin at much lower concentrations (∼7 mol %) leads to a decrease in the lateral diffusion coefficient of DOPC by a factor of 1.3 at lower temperatures and by a factor of 1.14 at higher temperatures. For DMPC, the diffusion coefficient decreases by a factor of 1.5 at lower temperatures and by a factor of 1.2 at higher temperatures. Further increasing the curcumin concentration has no effect. Comparison with cholesterol showed that curcumin and cholesterol influence lateral diffusion of lipids differently. The effect of curcumin is determined by its solubility in lipid bilayers, which is as low as 10 mol % that is much less than that of cholesteroĺs 66 mol %.

  • 124.
    Filippov, Andrei
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Kotenkov, Sergey A.
    Kazan (Volga Region) Federal University, Kazan, Institute of Physics, Kazan (Volga Region) Federal University.
    Munavirov, Bulat
    Kazan (Volga Region) Federal University, Kazan, Institute of Physics, Kazan (Volga Region) Federal University.
    Khaliulina, Aliya V.
    Institute of Physics, Kazan (Volga Region) Federal University.
    Gnezdilov, Oleg I.
    Kazan (Volga Region) Federal University, Kazan, Institute of Physics, Kazan (Volga Region) Federal University.
    Antzutkin, Oleg
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Effect of curcumin on lateral diffusion in lipid bilayers2016Inngår i: Mendeleev communications (Print), ISSN 0959-9436, E-ISSN 1364-551X, Vol. 26, nr 2, s. 109-110Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Lateral diffusion in dimyristoylphosphatidylcholine lipid bilayers decreases in the presence of cholesterol and curcumin, as measured by 1H NMR spectroscopy, but the mechanisms of action of these two compounds are different.

  • 125.
    Filippov, Andrei
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. Kazan State Medical University, Kazan, Russian Federation.
    Kurakin, S.
    Institute of Physics, Kazan Federal University, Kazan, Russian Federation.
    Gnezdilov, O.I.
    Institute of Physics, Kazan Federal University, Kazan, Russian Federation.
    Antzutkin, Oleg
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. Department of Physics, Warwick University, Coventry, United Kingdom.
    Effect of magnetic field on diffusion of ethylammonium nitrate: water mixtures confined between polar glass plates2018Inngår i: Journal of Molecular Liquids, ISSN 0167-7322, E-ISSN 1873-3166, Vol. 4, s. 45-51Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    We used 1H NMR diffusometry to study mixtures of ethylammonium nitrate (EAN) with water (3.1–12.4 mol% of added H2O) confined between polar glass plates and exposed to a static magnetic field of 9.4 T. The presence of such restrictions reverses the concentration dependence of the diffusivities of the EA (ethylammonium) cation and water typical for the bulk system. The presence of water weakens the effects of a static magnetic field on diffusion of the EA cation as well as on proton exchange of –NH3 groups. Surprisingly, the amplitude of the echo signal of water protons decreases during exposure to the magnetic field and finally disappears, a phenomenon that depends on the concentration of water in the system. Based on experimental data, we suggest that water in the system is present in two states with different dynamic properties. One type of water formed in confinement possesses NMR relaxation time typical for liquids; its diffusivity can be measured by 1H NMR. The second type of water is formed upon exposure of the sample of the first type to the magnetic field and eventually includes all the water in the system. This type of water possesses “solid-like” NMR relaxation features that makes it “invisible” to the NMR diffusometry technique. We suggest that this second type of water is adsorbed onto the glass plates. Correspondingly, EAN exists in two liquid phases: the first one contains an EAN-water mixture, while the second one contains neat EAN, and forms on the microscopic scale range under the influence of a static magnetic field.

  • 126.
    Filippov, Andrei
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Taher, Mamoun
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Shah, Faiz Ullah
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Glavatskih, Sergei
    Antzutkin, Oleg
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    The effect of the cation alkyl chain length on density and diffusion in dialkylpyrrolidinium bis(mandelato)borate ionic liquids2014Inngår i: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 16, nr 48, s. 26798-26805Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    The physicochemical properties of ionic liquids are strongly affected by the selective combination of the cations and anions comprising the ionic liquid. In particular, the length of the alkyl chains of ions has a clear influence on the ionic liquid's performance. In this paper, we study the self-diffusion of ions in a series of halogen-free boron-based ionic liquids (hf-BILs) containing bis(mandelato)borate anions and dialkylpyrrolidinium cations with long alkyl chains CnH2n+1 with n from 4 to 14 within a temperature range of 293-373 K. It was found that the hf-BILs with n = 4-7 have very similar diffusion coefficients, while hf-BILs with n = 10-14 exhibit two liquid sub-phases in almost the entire temperature range studied (293-353 K). Both liquid sub-phases differ in their diffusion coefficients, while values of the slower diffusion coefficients are close to those of hf-BILs with shorter alkyl chains. To explain the particular dependence of diffusion on the alkyl chain length, we examined the densities of the hf-BILs studied here. It was shown that the dependence of the density on the number of CH2 groups in long alkyl chains of cations can be accurately described using a "mosaic type" model, where regions of long alkyl chains of cations (named 'aliphatic' regions) and the residual chemical moieties in both cations and anions (named 'ionic' regions) give additive contributions. Changes in density due to an increase in temperature and the number of CH2 groups in the long alkyl chains of cations are determined predominantly by changes in the free volume of the 'ionic' regions, while 'aliphatic' regions are already highly compressed by van der Waals forces, which results in only infinitesimal changes in their free volumes with temperature.

  • 127.
    Garcia, Gustavo
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Synthesis of Zeolites from Bolivian Raw Materials for Catalysis and Detergency Applications2014Licentiatavhandling, med artikler (Annet vitenskapelig)
    Abstract [en]

    Zeolites are very useful in many technological applications such as catalysis, separation and purification of gases and solvents, ion-exchange, etc. The production of zeolites is nowadays carried out with a variety of reagents, such starting materials render large scale production of zeolites expensive. Hence alternative synthesis routes for zeolite production at a lower cost are currently under investigation. One of these routes involves the use of natural aluminosilicate raw materials which have many advantages such as their availability, low price, workability, etc. The aim of the present work was to provide routes to produce synthetic zeolites of industrial attractiveness derived from non-expensive Bolivian raw materials like clays and diatomites. In particular, the work was focused on the synthesis of intermediate- and low-silica zeolites: zeolite Y and zeolite A. The raw materials as well as intermediate materials and final zeolite products were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), nitrogen gas adsorption, inductively coupled plasma mass spectrometry (ICP-SFMS), and UV-VIS spectroscopy.The first part of the study addressed the synthesis and characterization of intermediate silica zeolite Y from diatomite. Prior to synthesis, the diatomite was leached in sulfuric acid to remove impurities, but this step also resulted in dealumination. Therefore, aluminum sulfate was used as an extra source of aluminum. The raw materials were reacted hydrothermally at 373 K in aqueous medium with sodium hydroxide. Variations in parameters like the Na2O/SiO2 ratio and synthesis time were investigated. As a result, micro-sized crystals of zeolite Y were obtained. It was possible to achieve high zeolite yield at a Na2O/SiO2 ratio of 0.9, which produced zeolite Y with a SiO2/Al2O3 ratio of 3.9. Also, synthesis of almost pure zeolite Y with a SiO2/Al2O3 ratio of 5.3 in low yield at a Na2O/SiO2 ratio of 0.6 was achieved. In this respect, diatomite behaved similarly to colloidal silica in traditional syntheses, with both sources of silica having a high degree of polymerization. Zeolite Y with the latter SiO2/Al2O3 ratio might be useful for the production of ultra-stable zeolite Y for use as FCC catalyst.A similar acid leaching procedure, this time with hydrochloric acid, was used for dealumination of diatomite to increase the SiO2/Al2O3 ratio and to reduce the amount of iron in producing well-crystallized ZSM-5 from diatomite in combination with sodium hydroxide and n-butyl amine under appropriate synthesis conditions.The second part of this study dealt with the synthesis of low silica zeolite A from Bolivian montmorillonite-type clay. This clay did contain significant amounts of quartz. Hence, an alkali fusion treatment was applied to the clay by fusing the clay at high temperature with NaOH to make the material more reactive and to take advantage of all the silica present in the clay. The raw clay had a SiO2/Al2O3 ratio of 4, and sodium aluminate was added to the mixture to decrease this ratio to 2. An optimization of the synthesis time was performed. The final zeolite product exhibited high brightness despite the presence of iron in appreciable amount in the starting material and the final product. This was attributed to the magnesium in the raw material, which exerted a masking effect on iron. The latter was incorporated into extraneous magnesium aluminosilica compounds, thereby increasing brightness and strongly decreasing the overall yellowness. This simple method appears as a promising alternative to the complex and costly techniques suggested to reduce the iron content in natural raw materials, especially kaolin.To summarize, this work reports the synthesis of zeolites with promising characteristics from Bolivian raw materials. However, further optimization is required to qualify these products for industrial applications. Moreover, this study might help in the development of poor regions of the Bolivian Altiplano and open up for large scale production, since the methods developed in this work are simple and non-expensiveand other impurities for synthesis of high silica ZSM-5 zeolite. This procedure was successful in producing well-crystallized ZSM-5 from diatomite in combination with sodium hydroxide and n-butyl amine under appropriate synthesis conditions.The second part of this study dealt with the synthesis of low silica zeolite A from Bolivian montmorillonite-type clay. This clay did contain significant amounts of quartz. Hence, an alkali fusion treatment was applied to the clay by fusing the clay at high temperature with NaOH to make the material more reactive and to take advantage of all the silica present in the clay. The raw clay had a SiO2/Al2O3 ratio of 4, and sodium aluminate was added to the mixture to decrease this ratio to 2. An optimization of the synthesis time was performed. The final zeolite product exhibited high brightness despite the presence of iron in appreciable amount in the starting material and the final product. This was attributed to the magnesium in the raw material, which exerted a masking effect on iron. The latter was incorporated into extraneous magnesium aluminosilica compounds, thereby increasing brightness and strongly decreasing the overall yellowness. This simple method appears as a promising alternative to the complex and costly techniques suggested to reduce the iron content in natural raw materials, especially kaolin.To summarize, this work reports the synthesis of zeolites with promising characteristics from Bolivian raw materials. However, further optimization is required to qualify these products for industrial applications. Moreover, this study might help in the development of poor regions of the Bolivian Altiplano and open up for large scale production, since the methods developed in this work are simple and non-expensive.

  • 128.
    Garcia, Gustavo
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Aguilar, Wilson
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Carabante, Ivan
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Geovetenskap och miljöteknik.
    Cabrera, Saúl
    Chemistry Research Institute IIQ, San Andres Mayor University UMSA, La Paz.
    Hedlund, Jonas
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Mouzon, Johanne
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Preparation of zeolite A with excellent optical properties from clay2015Inngår i: Journal of Alloys and Compounds, ISSN 0925-8388, E-ISSN 1873-4669, Vol. 619, s. 771-777Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Discoloration of zeolite A powder is a common problem when natural raw materials such as kaolin clay are used because of the formation of colored iron compounds. In this study, we report on a novel method to produce zeolite A with excellent optical properties, from clays. The brightness is as high as 94.5 and the yellowness is as low as 3.0. The product is comprised of intergrown zeolite A crystals with cubic habit and a length ranging between 0.5 and 2 μm. Good optical properties are obtained when the raw material contains magnesium, as some natural raw materials do, or alternatively, when a magnesium compound is added to the raw material. Magnesium probably forces iron inside colorless extraneous magnesium aluminosilicate compounds. This simple process appears very promising for the preparation of zeolite A with good optical properties from inexpensive natural raw materials.

  • 129.
    Garcia, Gustavo
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. Solid State and Theoretical Chemistry, Chemistry Research Institute, San Andres Mayor University.
    Cabrera, Saúl
    Solid State and Theoretical Chemistry, Chemistry Research Institute, San Andres Mayor University, University Campus.
    Hedlund, Jonas
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Mouzon, Johanne
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Selective synthesis of FAU-type zeolites2018Inngår i: Journal of Crystal Growth, ISSN 0022-0248, E-ISSN 1873-5002, Vol. 489, s. 36-41Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    In the present work, parameters influencing the selectivity of the synthesis of FAU-zeolites from diatomite were studied. The final products after varying synthesis time were characterized by scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction and gas adsorption. It was found that high concentrations of NaCl could completely inhibit the formation of zeolite P, which otherwise usually forms as soon as maximum FAU crystallinity is reached. In the presence of NaCl, the FAU crystals were stable for extended time after completed crystallization of FAU before formation of sodalite. It was also found that addition of NaCl barely changed the crystallization kinetics of FAU zeolite and only reduced the final FAU particle size and SiO2/Al2O3 ratio slightly. Other salts containing either Na or Cl were also investigated. Our results suggest that there is a synergistic effect between Na+ and Cl-. This is attributed to the formation of (Na4Cl)3+ clusters that stabilize the sodalite cages. This new finding may be used to increase the selectivity of syntheses leading to FAU-zeolites and avoid the formation of undesirable by-products, especially if impure natural sources of aluminosilica are used.

  • 130.
    Garcia, Gustavo
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Cardenas, Edgar
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Cabrera, Saúl
    Chemistry Research Institute IIQ, San Andres Mayor University UMSA, La Paz.
    Hedlund, Jonas
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Mouzon, Johanne
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Synthesis of zeolite Y from diatomite as silica source2016Inngår i: Microporous and Mesoporous Materials, ISSN 1387-1811, E-ISSN 1873-3093, Vol. 219, s. 29-37Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Bolivian diatomite was successfully used as a silica source for the synthesis of zeolite Y. Prior to synthesis, the diatomite was leached with sulfuric acid to remove impurities and aluminum sulfate was used as an aluminum source. The raw materials were reacted hydrothermally at 100 °C in water with sodium hydroxide and different Na2O/SiO2 ratios were investigated. The final products were characterized by scanning electron microscopy, X-ray diffraction, gas adsorption and inductively coupled plasma-atomic emission spectroscopy. Diatomites originating from different locations and therefore containing different types and amounts of minerals and clays as impurities were investigated. After optimization of synthesis time, zeolite Y with low SiO2/Al2O3 ratio (3.0–3.9) was obtained at a high yield for high alkalinity conditions (Na2O/SiO2 = 0.85–2.0). Lower Na2O/SiO2 ratios resulted in incomplete dissolution of diatomite and lower yield. Nevertheless, decreasing alkalinity resulted in a steady increase of the SiO2/Al2O3 ratio in zeolite Y. Consequently, it was possible to synthesize almost pure zeolite Y with a SiO2/Al2O3 ratio of 5.3 for a Na2O/SiO2 ratio of 0.6, albeit at a low yield. In this respect, diatomite enables the synthesis of high silica zeolite Y and behaves similarly to colloidal silica in traditional syntheses, with both sources of silica having in common a high degree of polymerization. Interestingly, the presence of minerals and clays in the starting diatomite had marginal effects on the outcome of the synthesis. However, their dissolution resulted in presence of calcium and magnesium in the zeolite Y crystals. Finally, overrun of all investigated compositions resulted in the formation of zeolite P nucleating and growing onto dissolving zeolite Y crystals, which was shown to be triggered when aluminum was completely depleted at high alkalinity

  • 131.
    Geng, Shiyu
    et al.
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Materialvetenskap.
    Shah, Faiz Ullah
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Liu, Peng
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Materialvetenskap.
    Antzutkin, Oleg
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Oksman, Kristiina
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Materialvetenskap.
    Plasticizing and crosslinking effects of borate additives on the structure and properties of poly(vinyl acetate)2017Inngår i: RSC Advances, ISSN 2046-2069, E-ISSN 2046-2069, Vol. 7, nr 13, s. 7483-7491Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    As an environmentally friendly, low-cost and widely used polymer, poly(vinyl acetate) (PVAc) is worth modifying to achieve better properties. Here, we report on the influence of borate additives on the structure and properties of partially hydrolysed PVAc. In addition to the general crosslinking function of borate additives, an extraordinary plasticizing effect was found. By controlling the pH from 4 to 11 during sample preparation, the plasticizing and crosslinking effects can be shifted. In alkaline conditions, the degree of crosslinking in the PVAc/borate sample is increased; however, this increase declines gradually with an increase in the borate additive content, which impacts the morphology of the PVAc latex particles, as well as the mechanical and thermal properties of the PVAc/borate films. In contrast, in acidic conditions, the PVAc/borate films are plasticized by borate additives; thus, their ultimate mechanical strength, elastic moduli and thermal stabilities decrease, while the water diffusivities increase.

  • 132.
    Geng, Shiyu
    et al.
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Materialvetenskap.
    Wei, Jiayuan
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Materialvetenskap.
    Jonasson, Simon
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Materialvetenskap.
    Hedlund, Jonas
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Oksman, Kristiina
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Materialvetenskap. Fibre and Particle Engineering, University of Oulu. Mechanical & Industrial Engineering (MIE), University of Toronto.
    Multifunctional Carbon Aerogels with Hierarchical Anisotropic Structure Derived from Lignin and Cellulose Nanofibers for CO2 Capture and Energy Storage2020Inngår i: ACS Applied Materials and Interfaces, ISSN 1944-8244, E-ISSN 1944-8252, Vol. 12, nr 6, s. 7432-7441Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    In current times, CO2 capture and light-weight energy storage are receiving significant attention and will be vital functions in next-generation materials. Porous carbonaceous materials have great potential in these areas, whereas most of the developed carbon materials still have significant limitations, such as non-renewable resources, complex and costly processing or the absence of tailorable structure. In this study, a new strategy is developed for using the currently under-utilized lignin and cellulose nanofibers, which can be extracted from renewable resources to produce high-performance multifunctional carbon aerogels with a tailorable, anisotropic pore structure. Both the macro- and microstructure of the carbon aerogels can be simultaneously controlled by discreetly tuning the weight ratio of lignin to cellulose nanofibers in the carbon aerogel precursors, which considerably influences their final porosity and surface area. The designed carbon aerogels demonstrate excellent performance in both CO2 capture and capacitive energy storage, and the best results exhibit a CO2 adsorption capacity of 5.23 mmol g-1 at 273 K and 100 kPa, and a specific electrical double layer capacitance of 124 F g-1 at a current density of 0.2 A g-1, indicating that they have great future potential in the relevant applications.

  • 133.
    Ginesy, Mireille
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Production of L-arginine by genetically modified Escherichia coli2015Licentiatavhandling, med artikler (Annet vitenskapelig)
    Abstract [en]

    In the recent years, the demand for environmental friendly produced L-arginine has risen with the increasing number of applications for this amino acid in pharmaceuticals, nutraceuticals, cosmetics, animal feed and fertilizers. Members of the Corynebacteriaceae family are usually used for microbial L-arginine production. However, Escherichia coli present the advantage of being able to utilize a wider range of substrates, including pentose sugars found in lignocellulosic feedstocks. The present thesis illustrates the first steps in the development of a sustainable process to produce L-arginine using E. coli. It starts with the constructions of a L-arginine overproducing strain, followed by optimization of the nitrogen supply for the fermentations.The first part of this thesis aimed at engineering an E. coli train able to produce high level of L-arginine. Mutations on key genes of the L-arginine biosynthesis pathway were step-wisely done. The mutants obtained at each step were tested in bioreactor fermentations to assess the effect of each genetic modification. The final strain was able to produce almost 12 g/l during fermentation, at a productivity of 0.24 g/l/h. In comparison the starting strain, E. coli K12 C600, was not able to excrete any L-arginine. To minimize nitrogen wastes and optimize the L-arginine production the impact of different nitrogen sources and concentration were investigated. It was shown that while ammonium phosphate dibasic was the most potent nitrogen source during cultivation on complex medium, all the sources were equivalent with minimal media; this probably reflected the phosphate deficiency of the complex medium used. In fermentation on minimal medium, a carbon to nitrogen ratio of 5 was demonstrated to be the most suitable, yielding up to 4.5 g/l L-arginine. At this ratio, both glucose and the nitrogen source were completely utilized during fermentation.

  • 134.
    Ginesy, Mireille
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Belotserkovsky, Jaroslav
    Department of Molecular Biosciences Wenner-Gren institute, Stockholm University.
    Enman, Josefine
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Isaksson, Leif
    Department of Molecular Biosciences Wenner-Gren institute, Stockholm University.
    Rova, Ulrika
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Metabolic engineering of Escherichia coli for enhanced arginine biosynthesis2015Inngår i: Microbial Cell Factories, ISSN 1475-2859, E-ISSN 1475-2859, Vol. 14, nr 1, artikkel-id 29Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    BackgroundArginine is a high-value product, especially for the pharmaceutical industry. Growing demand for environmental-friendly and traceable products have stressed the need for microbial production of this amino acid. Therefore, the aim of this study was to improve arginine production in Escherichia coli by metabolic engineering and to establish a fermentation process in 1-L bioreactor scale to evaluate the different mutants. ResultsFirstly, argR (encoding an arginine responsive repressor protein), speC, speF (encoding ornithine decarboxylases) and adiA (encoding an arginine decarboxylase) were knocked out and the feedback-resistant argA214 or argA215 were introduced into the strain. Three glutamate independent mutants were assessed in bioreactors. Unlike the parent strain, which did not excrete any arginine during glucose fermentation, the constructs produced between 1.94 and 3.03 g/L arginine. Next, wild type argA was deleted and the gene copy number of argA214 was raised, resulting in a slight increase in arginine production (4.11 g/L) but causing most of the carbon flow to be redirected toward acetate. The V216A mutation in argP (transcriptional regulator of argO, which encodes for an arginine exporter) was identified as a potential candidate for improved arginine production. The combination of multicopy of argP216 or argO and argA214 led to nearly 2-fold and 3-fold increase in arginine production, respectively, and a reduction of acetate formation. ConclusionsIn this study, E. coli was successfully engineered for enhanced arginine production. The ∆adiA, ∆speC, ∆speF, ∆argR, ∆argA mutant with high gene copy number of argA214 and argO produced 11.64 g/L of arginine in batch fermentation, thereby demonstrating the potential of E. coli as an industrial producer of arginine.

  • 135.
    Ginesy, Mireille
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Enman, Josefine
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Rusanova-Naydenova, Daniela
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Rova, Ulrika
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Simultaneous Quantification of L-Arginine and Monosaccharides during Fermentation: An Advanced Chromatography Approach2019Inngår i: Molecules, ISSN 1420-3049, E-ISSN 1420-3049, Vol. 24, nr 4, artikkel-id 802Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Increasing demand for L-arginine by the food and pharmaceutical industries has sparked the search for sustainable ways of producing it. Microbial fermentation offers a suitable alternative; however, monitoring of arginine production and carbon source uptake during fermentation, requires simple and reliable quantitative methods compatible with the fermentation medium. Two methods for the simultaneous quantification of arginine and glucose or xylose are described here: high-performance anion-exchange chromatography coupled to integrated pulsed amperometric detection (HPAEC-IPAD) and reversed-phase ultra-high-performance liquid chromatography combined with charged aerosol detection (RP-UHPLC-CAD). Both were thoroughly validated in a lysogeny broth, a minimal medium, and a complex medium containing corn steep liquor. HPAEC-IPAD displayed an excellent specificity, accuracy, and precision for arginine, glucose, and xylose in minimal medium and lysogeny broth, whereas specificity and accuracy for arginine were somewhat lower in medium containing corn steep liquor. RP-UHPLC-CAD exhibited high accuracy and precision, and enabled successful monitoring of arginine and glucose or xylose in all media. The present study describes the first successful application of the above chromatographic methods for the determination and monitoring of L-arginine amounts during its fermentative production by a genetically modified Escherichia coli strain cultivated in various growth media.

  • 136.
    Ginesy, Mireille
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Rusanova-Naydenova, Daniela
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Rova, Ulrika
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Tuning of the Carbon-to-Nitrogen Ratio for the Production of L-Arginine by Escherichia coli2017Inngår i: Fermentation, ISSN 2311-5637, Vol. 3, nr 4, artikkel-id 60Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    L-arginine, an amino acid with a growing range of applications within the pharmaceutical, cosmetic, food, and agricultural industries, can be produced by microbial fermentation. Although it is the most nitrogen-rich amino acid, reports on the nitrogen supply for its fermentation are scarce. In this study, the nitrogen supply for the production of l-arginine by a genetically modified Escherichia coli strain was optimised in bioreactors. Different nitrogen sources were screened and ammonia solution, ammonium sulphate, ammonium phosphate dibasic, and ammonium chloride were the most favourable nitrogen sources for l-arginine synthesis. The key role of the C/N ratio for l-arginine production was demonstrated for the first time. The optimal C/N molar ratio to maximise l-arginine production while minimising nitrogen waste was found to be 6, yielding approximately 2.25 g/L of l-arginine from 15 g/L glucose with a productivity of around 0.11 g/L/h. Glucose and ammonium ion were simultaneously utilized, showing that this ratio provided a well-balanced equilibrium between carbon and nitrogen metabolisms.

  • 137.
    Golets, M.
    et al.
    Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University.
    Shimpi, Manishkumar
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Wang, Y-L
    Applied Physical Chemistry, Department of Chemistry, KTH Royal Institute of Technology.
    Antzutkin, Oleg
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Glavatskih, Sergei
    System and Component Design, KTH, Royal Institute of Technology , Machine Design, KTH Royal Institute of Technology, SE-10044 Stockholm, Sweden, Department of Physics, Warwick University, Coventry.
    Laaksonen, Aatto
    Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University.
    Understanding the thermal decomposition mechanism of a halogen-free chelated orthoborate-based ionic liquid: a combined computational and experimental study2016Inngår i: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 18, s. 22458-22466Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    In the last few decades, ionic liquids (ILs) have gained significant attention as lubricants and lubricant additives due to their polar nature, low vapour pressure and tunable physicochemical properties. In this work, quantum chemistry calculations and atomistic Molecular Dynamics (MD) simulations were employed to predict thermal degradation mechanisms of a potential lubricating agent - the tributyloctylphosphonium bis(oxalato)borate ([P4,4,4,8][BOB]) IL. It was found that the onset of decomposition of the studied IL coincides with a cleavage of the B-O bonds in the [BOB](-) anion. Consequently, a series of chemical reactions of the [P4,4,4,8](+) cation with the [BOB](-) anion was triggered yielding alkylboranes, alkenes, trialkylphosphines, CO and CO2. Another ionic system, consisting of [P4,4,4,8][Cl], was also tested for a comparison. Thermogravimetric measurements have shown a higher thermal stability of [P4,4,4,8][BOB] compared to that of [P4,4,4,8][Cl] at least at the initial stage of decomposition, in accord with the presented calculations. Quantum chemical frequency calculations also agreed with the experimental Fourier Transform Infrared (FTIR) spectroscopy results.

  • 138.
    Gowda, Vasantha
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Combined experimental and theoretical studies of dithiocarbamate complexes of yttrium, lanthanum and bismuth2014Licentiatavhandling, med artikler (Annet vitenskapelig)
    Abstract [en]

    Metal-dithiocarbamate complexes find wide-ranging applications in nanomaterial and metalseparation science, and have potential use as chemotherapeutic, pesticides, and as additives tolubricants. A highly versatile dialkyldithiocarbamate (R2NCS2–) ligand can form stablecomplexes with all the transition elements and also the majority of main group, lanthanide andactinide elements. Here we present structural investigations of the molecular and electronicstructures of dialkyldithiocarbamate complexes with yttrium(III), lanthanum(III), andbismuth(III) of molecular formula [Y{S2CN(C2H5)2}3PHEN], [La{S2CN(C2H5)2}3PHEN], and[Bi2{S2CN-n(C4H9)2}6] (where PHEN=1,10-Phenanthroline) . The experimental solid-state 13Cand 15N cross polarization magic-angle-spinning (CP-MAS) NMR results are reported for allthese three complexes. We also report new single-crystal X-ray structures of heterolepticyttrium, lanthanum, and homoleptic bismuth dialkyldithiocarbamate complexes. Thecomparative analysis of powder XRD patterns and solid-state 13C and 15N CP-MAS spectra ofpolycrystalline yttrium(III) and lanthanum(III) diethyldithiocarbamato-phenanthrolinecomplexes shows the presence of significant structural differences. The diethyldithiocarbamatophenanthrolinecomplex of yttrium has a very similar structural type to a previously reported Xraydiffraction structure for [Nd{S2CN(C2H5)2}3PHEN] whereas, the crystal structure of[La{S2CN(C2H5)2}3PHEN] is considerably more complex. Our NMR and single-crystal X-raydiffraction results suggested polymorphism for bismuth di-n-butyldithiocarbamate complex.Finally, the experimental NMR results are complemented by chemical shifts obtained usingquantum chemical methods and verified the spectral assignments. Overall, our workdemonstrates how different experimental and theoretical methods can be combined that canafford insights into the solid-state structure and bonding environments of metal complexes.

  • 139.
    Gowda, Vasantha
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Experimental and Computational Magnetic Resonance Studies of Selected Rare Earth and Bismuth Complexes2017Doktoravhandling, med artikler (Annet vitenskapelig)
    Abstract [en]

    The rare-earth elements (REEs) and bismuth, being classified as the ‘most critical raw materials’ (European Raw Materials Initiatives, 2017), have a high economic importance to the EU combined with a high relative supply risk. REEs are highly important for the evolving technologies such as clean-energy applications, high-technology components, rechargeable batteries, permanent magnets, electric and hybrid vehicles, and phosphors monitors.This scientific research work aims at building a fundamental knowledge base concerning the electronic/molecular structure and properties of rare-earth element (REE) and bismuth complexes with dithiocarbamate (DTC) and 1,10-phenanthroline (PHEN) by employing state-of-the-art experimental techniques such as nuclear magnetic resonance (NMR) spectroscopy and X-ray diffraction (XRD) techniques together with ab initioquantum mechanical computational methods. This combination of methods has played a vital role in analysing the direct and significant effect of the heavy metal ions on the structural and magnetic resonance properties of the complexes, thereby, providing a framework of structure elucidation. This is of special importance for REEs, which are known to exhibit similar chemical and physical properties. The objectives of the work involve i) a systematic investigation of series of REE(III) as well as bismuth(III) complexes to get a profound understanding of the structure-properties relationship and ii) to find an appropriate theoretical modelling and NMR calculation methods, especially, for heavy metal systems in molecular and/or solid-state. This information can later be used in surface interaction studies of REE/bismuth minerals with DTC as well as in design and development of novel ligands for extraction/separation of metal ions.The REE(III) and bismuth(III) complexes with DTC and PHEN ligands have all provided aunique NMR fingerprint of the metal centre both in liquid and solid phase. The solid-state 13C and 15NNMR spectra of the diamagnetic REE(III) and bismuth(III) complexes were in accord with their structural data obtained by single crystal XRD. The density functional theory (DFT) methods were used to get complementary and refined structural and NMR parameters information for all diamagnetic complexes in the solid-state. The relativistic contributions due to scalar and spin-orbit correlations for the calculated 1H/13C/15N chemical shifts of REE complexes were analysed using two-component zeroth-order regular approximation (ZORA)/DFT while the ‘crystal-lattice’ effects on the NMR parameters were calculated by combining DFT calculations on molecular and periodic solid-state models. The paramagnetic REE complexes display huge differences in their 1H and 13C NMR spectral patterns. The experimental paramagnetic NMR (pNMR) chemical shifts, as well as the sizable difference of the 1H and 13C NMR shifts for these isoelectronic complexes, are well reproduced by the advanced calculations using ab initio/DFT approach. The accuracy of this approach is very promising for further applications to demanding pNMR problems involving paramagnetic f-block elements.The results presented in this thesis demonstrate that a multidisciplinary approach of combined experimental NMR and XRD techniques along with computational modelling and property calculations is highly efficient in studying molecular complexes and solids containing heavy metal systems, such as rare-earths and bismuth.

  • 140.
    Gowda, Vasantha
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Project: Solid-State NMR and DFT calculations on rare earth metal complexes2013Annet (Annet (populærvitenskap, debatt, mm))
  • 141.
    Gowda, Vasantha
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Laitinen, Risto S.
    Laboratory of Inorganic Chemistry, University of Oulu.
    Telkki, Ville-Veikko
    NMR Research Unit, University of Oulu.
    Larsson, Anna-Carin
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Antzutkin, Oleg
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Lantto, Perttu
    NMR Research Unit, University of Oulu.
    DFT calculations in the assignment of solid-state NMR and crystal structure elucidation of a lanthanum(iii) complex with dithiocarbamate and phenanthroline2016Inngår i: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 45, nr 48, s. 19473-19484Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    The molecular, crystal, and electronic structures as well as spectroscopic properties of a mononuclear heteroleptic lanthanum(iii) complex with diethyldithiocarbamate and 1,10-phenanthroline ligands (3 : 1) were studied by solid-state 13C and 15N cross-polarisation (CP) magic-angle-spinning (MAS) NMR, X-ray diffraction (XRD), and first principles density functional theory (DFT) calculations. A substantially different powder XRD pattern and 13C and 15N CP-MAS NMR spectra indicated that the title compound is not isostructural to the previously reported analogous rare earth complexes with the space group P21/n. Both 13C and 15N CP-MAS NMR revealed the presence of six structurally different dithiocarbamate groups in the asymmetric unit cell, implying a non-centrosymmetric packing arrangement of molecules. This was supported by single-crystal X-ray crystallography showing that the title compound crystallised in the triclinic space group P1[combining macron]. In addition, the crystal structure also revealed that one of the dithiocarbamate ligands has a conformational disorder. NMR chemical shift calculations employing the periodic gauge including projector augmented wave (GIPAW) approach supported the assignment of the experimental 13C and 15N NMR spectra. However, the best correspondences were obtained with the structure where the atomic positions in the X-ray unit cell were optimised at the DFT level. The roles of the scalar and spin-orbit relativistic effects on NMR shielding were investigated using the zeroth-order regular approximation (ZORA) method with the outcome that already the scalar relativistic level qualitatively reproduces the experimental chemical shifts. The electronic properties of the complex were evaluated based on the results of the natural bond orbital (NBO) and topology of the electron density analyses. Overall, we apply a multidisciplinary approach acquiring comprehensive information about the solid-state structure and the metal-ligand bonding of the heteroleptic lanthanum complex.

  • 142.
    Gowda, Vasantha
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Larsson, Anna-Carin
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Antzutkin, Oleg
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Lantto, Perttu
    University of Oulu.
    Modelling and structrual optimizations of rare earth coordination: First principles calculations2013Konferansepaper (Annet vitenskapelig)
    Abstract [en]

    An approximate 3D structure for the yttrium diethyldithiocarbamato-phenanthroline complex 1, obtained by manually replacing the Nd3+ ion with Y3+ion of the reported crystal structure for neodymium diethyldithiocarbamato-phenanthroline complex 2 followed by DFT geometry optimization using periodic boundary conditions with dispersion corrected functional, has been compared with DFT optimized structure for 1. The quality of the method is discussed by comparing predicted PXRD pattern, high resolution solid state 13C and 15N CP/MAS NMR data and calculated chemical shift tensor eigenvalues for optimized structures for 1 and 2. We have observed an excellent agreement between the ‘modeled’ and experimental structures. Finally, to take into account the relativistic effects on NMR shielding calculations, we have employed the zeroth-order regular approximation (ZORA) formalism using Slater-type orbital (STO) basis sets implemented in Amsterdam Density Functional (ADF) package. The present approach can be further extended to study other complexes of rare earth metals in general, particularly those having similar crystal structure.

  • 143.
    Gowda, Vasantha
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. NMR Research Unit, University of Oulu.
    Sarma, Bipul
    Department of Chemical Sciences, Tezpur University.
    Laitinen, Risto S.
    Laboratory of Inorganic Chemistry, University of Oulu.
    Larsson, Anna-Carin
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Ivanov, Alexander V.
    Institute of Geology and Nature Management, Far Eastern Branch of the Russian Academy of Sciences .
    Iuga, Dinu
    Department of Physics, Warwick University.
    Lantto, Perttu
    NMR Research Unit, University of Oulu.
    Antzutkin, Oleg
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. Department of Physics, Warwick University.
    Structural insights into the polymorphism of bismuth(III) di-n-butyldithiocarbamate by X-ray diffraction, solid-state (13C/15N) CP-MAS NMR and DFT calculations2017Inngår i: Polyhedron, ISSN 0277-5387, E-ISSN 1873-3719, Vol. 129, s. 123-132Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Two crystalline polymorphs of a binuclear tris(di-n-butyldithiocarbamato)bismuth(III) complex, I and II, with an empirical formula of [Bi{S2CN(n-C4H9)2}3] were synthesised and characterised by X-ray diffraction (XRD), solid-state NMR and density functional theory (DFT) calculations. At the supramolecular level, these mononuclear molecular units interact in pairs via secondary Bi⋯S bonds, yielding binuclear formations of [Bi2{S2CN(n-C4H9)2}6]. The polymorph I () contains two isomeric non-centrosymmetric binuclear molecules of [Bi2{S2CN(n-C4H9)2}6], which are related to each other as conformers, therefore having four structurally inequivalent bismuth atoms and twelve inequivalent dithiocarbamate ligands. In contrast, the structurally simpler polymorph II (P21/n) exists as a single molecular form of the corresponding centrosymmetric binuclear formation, comprising two structurally equivalent bismuth atoms and three structurally different dithiocarbamate groups. The polymorphs I and II were found to be interconvertible by altering the solvent system during the recrystallisation process. Sun et al. (2012) has reported a crystalline form of the title compound which resembles, but is not identical with, polymorph II. Experimental solid-state 13C and 15N cross-polarisation (CP) magic-angle-spinning (MAS) NMR spectra of both polymorphs I and II were in accord with the direct structural data on these complexes. Assignments of the resonance lines in the solid-state 13C and 15N NMR spectra were assisted by chemical shift calculations of the crystals using periodic DFT.

  • 144.
    Gowda, Vasantha
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Sarma, Bipul
    Department of Chemical Sciences, Division of Chemical Engineering, Tezpur University, Tezpur, Assam.
    Öberg, Sven
    Luleå tekniska universitet, Institutionen för teknikvetenskap och matematik, Materialvetenskap.
    Telkki, Ville-Veikko
    University of Oulu, NMR Research Group, Division of Chemical Engineering, Faculty of Science, University of Oulu.
    Larsson, Anna-Carin
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Lantto, Perttu
    University of Oulu, NMR Research Group, Division of Chemical Engineering, Faculty of Science, University of Oulu.
    Antzutkin, Oleg
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Structure Elucidation of an Yttrium Diethyldithiocarbamato-Phenanthroline Complex by X-ray Crystallography, Solid-State NMR, and ab-initio Quantum Chemical Calculations2016Inngår i: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-1948, Vol. 20, s. 3278-3291Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    We present a structural analysis method for molecular and electronic structure of yttrium diethyldithiocarbamato-phenanthroline complex {[Y(S2CNR2)3PHEN] with R = C2H5 and PHEN = 1,10-phenanthroline} combining solid-state NMR spectroscopy, XRD, and first principles DFT calculations. Replacing the Nd3+ ion with Y3+ in the reported crystal structure of [Nd(S2CNR2)3PHEN] complex generated an approximate 3D structure of the title complex. The structure was then subjected to first principles quantum chemical geometry optimisation using periodic DFT method. The quality of the method is discussed by comparing predicted and experimental powder XRD patterns. Full assignment of 13C and 15N solid-state CP-MAS NMR spectra as well as analyses of the principal values of the chemical shift tensors were carried out using periodic scalar relativistic DFT modelling. Spin-orbit relativistic effects, estimated by SO-ZORA formalism for one molecular unit, were evaluated. Finally, the X-ray structure of the title complex was determined, which proved that the former procedure is appropriate. The most important orbital interactions were investigated by Natural Bond Orbital analysis. The isotropic shielding values for S2CN-carbons were analysed by Natural Localised Molecular Orbital analysis. The present approach can be further extended to study other rare earth metal complexes, particularly those having similar but not yet solved crystal structures

  • 145.
    Grahn, Mattias
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Faisal, Abrar
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. Department of Chemical Engineering, COMSATS University Islamabad, Lahore Campus, Lahore, Pakistan.
    Öhrman, Olov G.W
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. RISE ETC - Energy Technology Center, SE-941 28 Piteå, Sweden.
    Zhou, Ming
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Signorile, Matteo
    Department of Chemistry, NIS and INSTM Reference Centre, Università di Torino, Torino, Italy.
    Crocellà, Valentina
    Department of Chemistry, NIS and INSTM Reference Centre, Università di Torino, Torino, Italy.
    Nabavi, Mohammad Sadegh
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Hedlund, Jonas
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Small ZSM-5 crystals with low defect density as an effective catalyst for conversion of methanol to hydrocarbons2019Inngår i: Catalysis Today, ISSN 0920-5861, E-ISSN 1873-4308Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    This work presents the synthesis of nearly defect-free ZSM-5 nanosized crystals, prepared in fluoride medium by seeding with silicalite-1. This material was carefully characterized and its catalytic performances in the methanol to hydrocarbons (MTH) reaction were assessed. Such fluoride-based material was compared to a reference ZSM-5, produced through a conventional alkaline synthesis but from the same seeding. Despite both the materials show closely identical morphology and they have a comparable acid site population, the catalyst prepared using the fluoride route showed significantly longer lifetime in MTH compared to the catalyst prepared using conventional synthesis at high pH. The slower deactivation for the samples prepared using the fluoride route was ascribed, thanks to a thorough in situ IR spectroscopy study, to its lower density of internal defects. According to the UV-Raman characterization of coke on the spent catalyst, the fluoride-based ZSM-5 catalyst produces less molecular coke species, most probably because of the absence of enlarged cavities/channels as due to the presence of internal defects. On the basis of these observations, the deactivation mechanism in the ZSM-5 synthesized by fluoride medium could be mostly related to the deposition of an external layer of bulk coke, whereas in the alkali-synthesized catalyst an additional effect from molecular coke accumulating within the porous network accelerates the deactivation process.

  • 146.
    Grahn, Mattias
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Hedlund, Jonas
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Maxwell-Stefan modelling of High flux tubular silicalite-1 membranes for CO2 removal from CO2/H2 gas mixtures2014Inngår i: Journal of Membrane Science, ISSN 0376-7388, E-ISSN 1873-3123, Vol. 471, s. 328-337Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    In this work, a Maxwell-Stefan model for high flux tubular silicalite-1 membranes for separation of CO2 from a CO2/H2 mixture was developed. The model concerns tubular membranes operating in a counter flow module and includes transport through flow-through defects in the silicalite-1 film and pressure drop over the graded alumina support. Adsorption and diffusion parameters for perfect silicalite-1 crystals were taken from literature. The flux and selectivity predicted by the model were in reasonably good agreement with experimentally observed data for a ZSM-5 membrane without any fitting of the model. However, the CO2 flux and selectivity measured experimentally for the ZSM-5 membrane were higher than that predicted by the model for a silicalite-1 membrane.The model was used to investigate a case with a 20 000 Nm3/d feed comprised of a 50/50 mixture of CO2/H2 at pressure of 25 bar and a membrane temperature of 296 K. The permeate pressure was 1 bar and 90% of the CO2 permeated the membrane. In this case, the membrane permselectivity and CO2 flux varied along the length of the tubes between 20–26 and 950–396 kg/(m2 h), respectively. Further, both defects and pressure drop over the support were shown to have an adverse effect on the selectivity, which indicates that membrane selectivity can be improved by reducing the flow-through defects and/or by preparing supports with less flow resistance. For a one-stage process, the required membrane area is as small as ca 0.85 m2 and the hydrogen loss through the membrane was 12.4%. For a two-stage process the required membrane area almost doubled to 1.6 m2, however the hydrogen loss through the second membrane is reduced to as little as 2.5%. In summary, this work shows that high flux zeolite membranes may be an interesting option for CO2 removal from synthesis gas.

  • 147.
    Grahn, Mattias
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Higman, Christopher
    HigmanConsulting GmbH.
    Holmgren, Allan
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. ZeoMemSweden AB.
    Hedlund, Jonas
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. ZeoMemSweden AB.
    Efficient syngas upgrading with high flux zeolite membranes2017Inngår i: 34th Annual International Pittsburgh Coal Conference: Coal - Energy, Environment and Sustainable Development, PCC 2017, International Pittsburgh Coal Conference , 2017Konferansepaper (Fagfellevurdert)
  • 148.
    Gusain, Rashi
    et al.
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik. Chemical Science Division, CSIR-Indian Institute of Petroleum, Dehradun.
    Panda, Somenath
    Department of Chemistry, Indian Institute of Technology Madras, Chennai.
    Bakshi, Paramjeet Singh
    Chemical Science Division, CSIR-Indian Institute of Petroleum, Dehradun.
    Gardas, Ramesh L.
    Department of Chemistry, Indian Institute of Technology Madras, Chennai.
    Khatri, Om Prakash
    Chemical Science Division, CSIR-Indian Institute of Petroleum, Dehradun.
    Thermophysical properties of trioctylalkylammonium bis(salicylato)borate ionic liquids: Effect of alkyl chain length2018Inngår i: Journal of Molecular Liquids, ISSN 0167-7322, E-ISSN 1873-3166, Vol. 269, s. 540-546Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Thermophysical properties of halogen-free ionic liquids are gaining significant attention for industrial applications. In this context, trioctylalkylammonium bis(salicylato)borate (N888n-BScB) ionic liquids having variable alkyl chain length (n = 4, 8, 12, 16) are synthesized to explore the effect of chain length and temperature on their physicochemical properties. The density (ρ), refractive index (nD), and speed of sound (u) are measured in the temperature range of 293.15 to 333.15 K. The tetraoctylammonium-BScB is found to be highly dense ionic liquid, and it was attributed to the closer packing of symmetric structure of tetraoctylammonium cation. Furthermore, derived thermodynamic properties such as isentropic compressibility (βs), coefficient of thermal expansion (α), standard entropy (S°), intermolecular free length (Lf) and lattice energy (UPOT) are calculated for the N888n-BScB ionic liquids using the experimental data and shown the effect of variable chain length. This study provides a comprehensive insight on the thermophysical properties of halogen-free ionic liquids.

  • 149.
    Hafeez, Abdul
    et al.
    Department of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan.
    Akhter, Zareen
    Department of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan.
    Gallagher, John F.
    School of Chemical Sciences, Dublin City University, Glasnevin, Dublin, Ireland.
    Khan, Nawazish Ali
    Materials Science Laboratory, Department of Physics, Quaid-i-Azam University, Islamabad, Pakistan.
    Gul, Asghari
    Department of Chemistry, COMSATS University, Islamabad, Pakistan.
    Shah, Faiz Ullah
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Synthesis, Crystal Structures, and Spectroscopic Characterization of Bis-aldehyde Monomers and Their Electrically Conductive Pristine Polyazomethines2019Inngår i: Polymers, ISSN 2073-4360, E-ISSN 2073-4360, Vol. 11, nr 9, artikkel-id 1498Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Bis-aldehyde monomers 4-(4′-formyl-phenoxy)benzaldehyde (3a), 3-methoxy-4-(4′-formyl-phenoxy)benzaldehyde (3b), and 3-ethoxy-4-(4′-formyl-phenoxy)benzaldehyde (3c) were synthesized by etherification of 4-fluorobenzaldehyde (1) with 4-hydroxybenzaldehyde (2a), 3-methoxy-4-hydroxybenzaldehyde (2b), and 3-ethoxy-4-hydroxybenzaldehyde (2c), respectively. Each monomer was polymerized with p-phenylenediamine and 4,4′-diaminodiphenyl ether to yield six poly(azomethine)s. Single crystal X-ray diffraction structures of 3b and 3c were determined. The structural characterization of the monomers and poly(azomethine)s was performed by FT-IR and NMR spectroscopic techniques and elemental analysis. Physicochemical properties of polymers were investigated by powder X-ray diffraction, thermogravimetric analysis (TGA), viscometry, UV–vis, spectroscopy and photoluminescence. These polymers were subjected to electrical conductivity measurements by the four-probe method, and their conductivities were found to be in the range 4.0 × 10−5 to 6.4 × 10−5 Scm−1, which was significantly higher than the values reported so far.

  • 150.
    Hall, Colin J.
    et al.
    Ian Wark Research Institute, University of South Australia.
    Ponnusamy, Thirunavukkarasu
    Ian Wark Research Institute, University of South Australia.
    Murphy, Peter J.
    Mawson Institute, University of South Australia.
    Lindberg, Mats
    Antzutkin, Oleg
    Luleå tekniska universitet, Institutionen för samhällsbyggnad och naturresurser, Kemiteknik.
    Griesser, Hans J.
    Mawson Institute, University of South Australia.
    A solid-state nuclear magnetic resonance study of post-plasma reactions in organosilicone microwave plasma-enhanced chemical vapor deposition (PECVD) coatings2014Inngår i: ACS Applied Materials and Interfaces, ISSN 1944-8244, E-ISSN 1944-8252, Vol. 6, nr 11, s. 8353-8362Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Plasma-polymerized organosilicone coatings can be used to impart abrasion resistance and barrier properties to plastic substrates such as polycarbonate. Coating rates suitable for industrial-scale deposition, up to 100 nm/s, can be achieved through the use of microwave plasma-enhanced chemical vapor deposition (PECVD), with optimal process vapors such as tetramethyldisiloxane (TMDSO) and oxygen. However, it has been found that under certain deposition conditions, such coatings are subject to post-plasma changes; crazing or cracking can occur anytime from days to months after deposition. To understand the cause of the crazing and its dependence on processing plasma parameters, the effects of post-plasma reactions on the chemical bonding structure of coatings deposited with varying TMDSO-to-O2 ratios was studied with 29Si and 13C solid-state magic angle spinning nuclear magnetic resonance (MAS NMR) using both single-pulse and cross-polarization techniques. The coatings showed complex chemical compositions significantly altered from the parent monomer. 29Si MAS NMR spectra revealed four main groups of resonance lines, which correspond to four siloxane moieties (i.e., mono (M), di (D), tri (T), and quaternary (Q)) and how they are bound to oxygen. Quantitative measurements showed that the ratio of TMDSO to oxygen could shift the chemical structure of the coating from 39% to 55% in Q-type bonds and from 28% to 16% for D-type bonds. Post-plasma reactions were found to produce changes in relative intensities of 29Si resonance lines. The NMR data were complemented by Fourier transform infrared (FTIR) spectroscopy. Together, these techniques have shown that the bonding environment of Si is drastically altered by varying the TMDSO-to-O2 ratio during PECVD, and that post-plasma reactions increase the cross-link density of the silicon-oxygen network. It appears that Si-H and Si-OH chemical groups are the most susceptible to post-plasma reactions. Coatings produced at a low TMDSO-to-oxygen ratio had little to no singly substituted moieties, displayed a highly cross-linked structure, and showed less post-plasma reactions. However, these chemically more stable coatings are less compatible mechanically with plastic substrates, because of their high stiffness

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