Lithium transition metal (Ti, Nb, V) oxide mesoporous thin films: contrasting results when attempting direct synthesis by evaporation-induced self assemblyCaes, Sébastien ; Malherbe, Cédric ; Krins, Natacha et alin Microporous & Mesoporous Materials (2013), 172 This work investigates the possibility to prepare mesoporous thin films of Li-Ti, Li-Nb, Li-Nb-V and Li-V oxides through a direct sol-gel EISA route by dissolving a lithium salt in the precursor solution ... [more ▼] This work investigates the possibility to prepare mesoporous thin films of Li-Ti, Li-Nb, Li-Nb-V and Li-V oxides through a direct sol-gel EISA route by dissolving a lithium salt in the precursor solution. Experimental conditions involve a hydrolysis molar ratio H2O/TM ~10 (TM = Ti,Nb,V) and the common Pluronic structuring agent P123 (EO20-PO70-EO20). Systematic formation of lithium-containing oxides as first-crystallizing phases points to a significant intermixture of lithium and transition metal ions in the inorganic network. In the case of Ti-based and Nb-based oxide films, addition of lithium to the precursor solution is compatible with the formation of amorphous mesoporous films at 350°C. On the contrary, addition of lithium has a detrimental effect on the notoriously difficult formation of vanadium-based mesostructured films: even when replacing half of the vanadium by niobium as a stabilizer, formation of mesostructured films has not been possible in the investigated range of experimental conditions. [less ▲] Detailed reference viewed: 29 (17 ULg) Development of a quantitative approach to measure phospholipids in dried drops by Raman spectroscopyMalherbe, Cédric ; ; Gilbert, Bernard et alPoster (2012, October) We present here the results obtained during our tentative to analyse quantitatively dried drops of phospholipidic solutions by Raman spectroscopy. Drops of different solutions of phospholipid were deposed ... [more ▼] We present here the results obtained during our tentative to analyse quantitatively dried drops of phospholipidic solutions by Raman spectroscopy. Drops of different solutions of phospholipid were deposed onto different material supports. The spots were then analyses by confocal Raman microspectroscopy. Experimental settings have been optimised and the analysis of the intensity profile of the Raman signal inside the spot allows the establishment of a calibration curve for the determination of the phospholipids amount within a 1 µL solution. [less ▲] Detailed reference viewed: 20 (5 ULg) Synthesis and characterization of recyclable chemically cross-linked shape memory materialsDefize, Thomas ; Riva, Raphaël ; Thomassin, Jean-Michel et alConference (2012, September 10) Detailed reference viewed: 10 (4 ULg) Online monitoring of heterogeneous polymerizations in supercritical carbon dioxide by Raman spectroscopyGrignard, Bruno ; Gilbert, Bernard ; Malherbe, Cédric et alin Chemphyschem : A European Journal of Chemical Physics and Physical Chemistry (2012), 13(11), 2666-2670 A novel setup is described to monitor the kinetics of homogeneous and heterogeneous reactions online using Raman spectroscopy under high pressure. The arrangement is based on a high-pressure reactor ... [more ▼] A novel setup is described to monitor the kinetics of homogeneous and heterogeneous reactions online using Raman spectroscopy under high pressure. The arrangement is based on a high-pressure reactor equipped with a sapphire window in combination with a mobile probe that allows the collection of the back-scattered Raman signal at 360°. [less ▲] Detailed reference viewed: 33 (13 ULg) Determination of the composition of cryolitic melts involved in the Hall-Heroult process by Raman spectroscopyMalherbe, Cédric ; Gilbert, Bernard ![]() Conference (2012, August) Considering our experience in the study of such highly corrosive media by Raman spectroscopy and since the bath spectrum is function of the molar NaF/AlF3 ratio and the Al2O3 content, we have proposed in ... [more ▼] Considering our experience in the study of such highly corrosive media by Raman spectroscopy and since the bath spectrum is function of the molar NaF/AlF3 ratio and the Al2O3 content, we have proposed in the past to apply that technique to the direct determination of the melt composition . Recent instrumental developments on CCD based spectrometers have made the proposed method more feasible. This presentation will first demonstrate that, employing an updated instrument provided with new optical filters and a more sensitive CCD detector, better quality spectra are obtained. Afterward, new results relevant to the development of our analytical method for the direct determination of the molar NaF/AlF3 ratio and the Al2O3 content in cryolitic melt will be discuss. Different aspects of the calculation procedure will be illustrated: Estimation and subtraction method of the Rayleigh decay from melt spectra; Development of an internal normalisation procedure based on equilibria in the melt and assisted by home-made software; Establishment of calibration curves for the determination of the molar ratio NaF/AlF3 in the melt; Establishment of calibration curves for the determination of oxide content in the melt; Overall procedure for the composition determination. [less ▲] Detailed reference viewed: 15 (1 ULg) Determination of the composition of cryolitic melts involved in the Hall-Heroult process by Raman spectroscopyMalherbe, Cédric ; Eppe, Gauthier ; Gilbert, Bernard ![]() Poster (2012, August) Detailed reference viewed: 9 (2 ULg) Raman spectroscopy, a tool for biochemical applicationsMalherbe, Cédric ![]() Scientific conference (2012, April 17) Detailed reference viewed: 7 (1 ULg) Charged poly(D,L-lactide) nanofibers: towards customized surface propertiesCroisier, Florence ; Aqil, Abdelhafid ; Malherbe, Cédric et alin Macromolecular Symposia (2011), 309/310(1), 20-27 Surface-charged nanofibers were prepared by electrospinning technique (ESP). For this purpose, a copolymer bearing carboxylic acid functions was added to a poly(D,L-lactide) solution just before ESP ... [more ▼] Surface-charged nanofibers were prepared by electrospinning technique (ESP). For this purpose, a copolymer bearing carboxylic acid functions was added to a poly(D,L-lactide) solution just before ESP process. In a basic medium, negative charges were therefore revealed on fiber surface. By deposition of positively charged particles or polyelectrolytes, surface properties of the fibers could be tailor-made for a specific application. This versatile method can, for example, be applied to the preparation of new biomedical scaffolds. [less ▲] Detailed reference viewed: 32 (14 ULg) To the determination of alumina content in cryolithic melt by Raman spectroscopyMalherbe, Cédric ![]() Poster (2011) Detailed reference viewed: 11 (2 ULg) Development of an analytical method to determine the cryolitic bath composition by Raman spectroscopyMalherbe, Cédric ; Gilbert, Bernard ![]() Poster (2010, April 23) Since the end of the nineteenth century, metallic aluminium is produced by electro-deposition from a solution of aluminium oxide in cryolitic melts around 1000°C (Hall-Héroult process). The industrial ... [more ▼] Since the end of the nineteenth century, metallic aluminium is produced by electro-deposition from a solution of aluminium oxide in cryolitic melts around 1000°C (Hall-Héroult process). The industrial melt is composed mostly of cryolite (Na3AlF6) and AlF3 and is characterized by the molar NaF/AlF3 ratio, named cryolitic ratio (CR). It turns out that the bath composition is critical: for instance, it has been shown that a small change in the Al2O3 content leads to a great change in the overvoltage required for the electrolysis. Therefore controlling the melt composition is very important in order to reduce the energy lost. Unfortunately no in situ analytical method allows studying the composition of the melt yet. Considering our experience in the study of such highly corrosive media by Raman spectroscopy and since the bath spectrum is function of both the CR and the Al2O3 content, we have proposed in the past to apply that technique to the direct determination of the melt composition. Despite the CR could be well evaluated in the lab, experimental problems however made the practical application difficult. The purpose of this presentation will be to show the new results obtained on an updated instrument: - Spectra are recorded in 20 s or less with a higher quality than before. - The previously developed home-made software was adapted to the updated instrument and various spectra analysis procedures are under study. - A procedure to prepare reference samples was also developed taking into account the homogeneity problems that have been met. - The slopes of the alumina calibration curves are depending on the bath CR, in confirmation of our previous results. - The new results are compared with the previous ones. It will be concluded that Raman spectroscopy is indeed becoming a suitable technique for developing an analytical method to determine the composition of industrial cryolitic melts. [less ▲] Detailed reference viewed: 20 (4 ULg) The Hydrogen Electrode in Ionic Liquids: Acidity Measurements and TitrationsRobert, Thierry ; Malherbe, Cédric ; et alPoster (2010, March) The acidity level in ILs containing acid was first determined using the Hammett acidity function (H0)1-2 in our laboratory. It was demonstrated that this attainable acidity, extending from -3 to -8, is ... [more ▼] The acidity level in ILs containing acid was first determined using the Hammett acidity function (H0)1-2 in our laboratory. It was demonstrated that this attainable acidity, extending from -3 to -8, is exclusively depending of the nature of anion and follow the order: PF6 > BF4 > NTf2 > OTf. Nevertheless, the Hammett acidity function is an apparent function in this media and must then be corrected for. Consequently, in a second step, we tried to evaluate directly the proton activity from the determination of a potentiometric acidity function (R0) based on the extrathermodynamic Strehlow assumption.3 Therefore, the equilibrium potential of the H+/H2 couple was measured with an hydrogen electrode versus the ferricinium/ferrocene couple for which the potential is considered as independent of the solvent. [less ▲] Detailed reference viewed: 107 (5 ULg) An analytical method to determine the composition of cryolitic melts involved in the Hall-Heroult process by Raman spectroscopyMalherbe, Cédric ; Gilbert, Bernard ![]() Poster (2010, March) The Hall-Héroult process involves the metallic aluminium production from electroreduction of aluminium oxide in cryolitic melt (mostly composed of cryolite and aluminium fluoride) around 1000°C. In order ... [more ▼] The Hall-Héroult process involves the metallic aluminium production from electroreduction of aluminium oxide in cryolitic melt (mostly composed of cryolite and aluminium fluoride) around 1000°C. In order to reduce the energy loss during this process, controlling the melt composition turns out to be critical. Unfortunately, no in situ analytical method allows measuring the melt composition yet. Since the Raman spectrum of the melt depends on both the cryolitic ratio (molar NaF/AlF3 ratio, CR) and the aluminium oxide content, our laboratory proposed in the past to apply Raman spectroscopy for direct melt composition determination by recording the spectrum from the top. However, experimental problems made the practical application difficult. Nowadays, the method is becoming more feasible because of new instrumental developments such as new sensitive CCD, fiber optics and new optical filters. [less ▲] Detailed reference viewed: 30 (0 ULg) Tentative determination of the acidity level in room temperature ionic liquids by electrochemical methodsMalherbe, Cédric ; Robert, Thierry ; et alin ECS Transactions (2009), 16(49), 3 In our attempt to evaluate the acidity levels reached by acidified ionic liquids (BMImBF4, BMImNTf2 and BMImOTf + HOTf or HNTf2), the uncertainty on the pKas of the indicators needed for the Hammett ... [more ▼] In our attempt to evaluate the acidity levels reached by acidified ionic liquids (BMImBF4, BMImNTf2 and BMImOTf + HOTf or HNTf2), the uncertainty on the pKas of the indicators needed for the Hammett spectrophotometric procedure was pointed out. As consequence another method is proposed, based on the H+/H2 couple potential measurement. In this purpose, if dynamic methods failed mainly for lack of sufficient reversibility, potentiometry with a hydrogen electrode gave meaningful results. The R0(H+) Strehlow function, could be calculated, using the Fc+-Fc couple as reference assumed as solvent independent. The obtained results show that i) the acidities are much higher than those in water; ii) the acidities measured by the hydrogen electrode are higher than those measured by the Hammett method; iii) the sequence of acidities for solutions of similar content of added acid is still BF4 > NTf2 > OTf as previously measured with the Hammett method. [less ▲] Detailed reference viewed: 25 (9 ULg) |
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