References of "Gilbert, Bernard"
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See detailFading of modern Prussian blue pigments in linseed oil medium
Samain, Louise ULg; Silversmit, Geert; Sanyova, Jana et al

in Journal of Analytical Atomic Spectrometry [=JAAS] (2011), 26(5), 930

The fading of modern laboratory-synthesized and commercial Prussian blue, iron(III) hexacyanoferrate(II), based pigments in a linseed oil medium during exposure to light has been investigated. The ... [more ▼]

The fading of modern laboratory-synthesized and commercial Prussian blue, iron(III) hexacyanoferrate(II), based pigments in a linseed oil medium during exposure to light has been investigated. The Prussian blue pigments were painted from linseed oil, as a pure pigment and mixed with white lead, (PbCO3)2Pb(OH)2, zinc white, ZnO, or titanium white, TiO2, pigment. The samples were subjected to accelerated ageing for 800 hours and the light fastness of the Prussian blue pigment was evaluated by reference to blue wool standards. Pure Prussian blue is extremely light fast whilst it strongly fades when mixed with a white pigment, especially with lead white or zinc oxide. The painted samples were studied by UV-visible, iron K-edge X-ray absorption, iron-57 transmission Mössbauer, and attenuated total reflectance infrared spectroscopy. X-ray absorption results reveal a decrease in the iron coordination number in aged samples in the presence of white pigment. The Mössbauer spectra of the pure Prussian blue and the unaged and aged mixtures of Prussian blue and lead white or zinc oxide at 1:100 and 1:10 dilution ratios, respectively, indicate the presence of iron(II) and iron(III) in a ratio close to one as expected for the bulk stoichiometric KFeIII[FeII(CN)6]; no change in the spectral parameters was observed upon ageing. Combined with the X-ray near edge absorption and infrared studies, these results suggest reduction of the surface iron ions in the Prussian blue with ageing upon exposure to light. [less ▲]

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See detailStraightforward synthesis of conductive graphene/polymer nanocomposites from graphite oxide
Vuluga, Daniela ULg; Thomassin, Jean-Michel ULg; Molenberg, Isabel et al

in Chemical Communications (2011), 47

The reduction of graphite oxide (GO) in the presence of reactive poly(methyl methacrylate) (PMMA), under mild biphasic conditions, directly affords graphene grafted with PMMA. The resulting nanocomposite ... [more ▼]

The reduction of graphite oxide (GO) in the presence of reactive poly(methyl methacrylate) (PMMA), under mild biphasic conditions, directly affords graphene grafted with PMMA. The resulting nanocomposite shows excellent electrical conductivities resulting from the optimal dispersion and exfoliation of graphene in the polymer matrix. [less ▲]

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See detailHammett Acidity Scale in Ionic Liquids : An Indication of Their Weak Dissociating Character
Robert, Thierry ULg; Magna, Lionel; Olivier-Bourbigou, Hélène et al

Poster (2010, August)

Ionic liquids are salts with the particularity to exhibit melting points near room temperature (below 100°C, by convention) with no vapour tension. For this last reason, ionic liquids are sometimes called ... [more ▼]

Ionic liquids are salts with the particularity to exhibit melting points near room temperature (below 100°C, by convention) with no vapour tension. For this last reason, ionic liquids are sometimes called “green solvents”. In addition, their exclusive materials and solvent properties has led to an amazing increase of interest from both academic and industrial community, confirmed by the explosion of the number of published papers in the last decade. The many combinations of organic and inorganic cations and anions allow an infinity of new ionic solvents then permitting the selection of the desired properties for a given application. Nevertheless, it is impossible to investigate all these combinations and the unusual complexity of these new solvents gives rise to many controversies. Consequently, the development of the general rules for understanding the chemistry in ionic liquids is crucial. A fundamental property of solvent is its solvating power, for instance towards the proton. Therefore, we are interested to investigate the acid-base properties in ionic liquids in order to ultimately find a correlation with the acidic catalysis activity. We then have proposed a colorimetric method to determine the acidity levels accessible in these new media: the Hammett acidity function H0. This spectroscopic method is based on the protonation equilibrium for a family of coloured indicator with pKa’s assumed as solvent independent (following the Hammett proposition). This presentation will summarize our Hammett acidity measurements in several ionic liquids. - At first, we will show that it is possible to evaluate the Hammett acidity function with two different coloured indicators, in the same ionic liquid. Since the Hammett acidity of a given mixture was found to depend on the choosen coloured indicator, this suggests the formation of ions associations in ionic liquids. As a result, the ionic liquids are clearly not as dissociating as initially thought and the Hammett acidity function is in fact an apparent function, underestimating the real acidity level. - The apparent acidity functions have then been compared for several ionic liquids to which an acid has been added ([BMIm][NTf2], [BMIm][BF4], [BMIm][OTf], [BHIm][NTf2], [BMIm][PF6], [HNEt3][NTf2]). The conclusions are as follows: 1) the accessible acidity level is not influenced by the nature of the cation; 2) on the contrary, the nature of anion is very critical and the solvating power towards the proton follows the order: OTf- > NTf2- > BF4- > PF6-. The more the proton is solvated, the less it is acidic. - Finally, the difference of acidity of two acids, HOTf and HNTf2 (both strong acids in water), has been investigated in [BMIm][BF4], [BMIm][NTf2] and [BMIm][OTf]. In [BMIm][OTf], these two acids show the same acidity (they behave as strong acids) due to the solvent levelling effect; on the other hand, in [BMIm][NTf2] and [BMIm][BF4] allowing higher acidity levels, HNTf2 is stronger than HOTf . The observed difference is also another indication of the lower proton solvation in [BMIm][BF4] or [BMIm][NTf2] versus that in [BMIm][OTf]. [less ▲]

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See detailDevelopment of an analytical method to determine the cryolitic bath composition by Raman spectroscopy
Malherbe, Cédric ULg; Gilbert, Bernard ULg

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 ▲]

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See detailQuantitative Evaluation of Imputities in Ionic Liquids
Robert, Thierry ULg; Olivier-Bourbigou, Hélène; Gilbert, Bernard ULg

Poster (2010, March)

Since several years, our laboratory is studying the acidity in ionic liquids and showed that very acidic levels can be reached in these media when a strong acid is added. These acidity levels were ... [more ▼]

Since several years, our laboratory is studying the acidity in ionic liquids and showed that very acidic levels can be reached in these media when a strong acid is added. These acidity levels were determined using Hammett acidity1 (spectroscopic method) and Strehlow acidity2 (potentiometric method) measurements. Considering the attainable acidity levels, it turns out that the purity of these ionic solvents is very critical because all impurities (i.e methylimidazole, water, acetone, chloride …) can act as (strong) bases. Therefore, it is imperative to quantify these impurities to obtain reproducible results. [less ▲]

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See detailThe Hydrogen Electrode in Ionic Liquids: Acidity Measurements and Titrations
Robert, Thierry ULg; Malherbe, Cédric ULg; Magna, lionel et al

Poster (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 ▲]

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See detailAn analytical method to determine the composition of cryolitic melts involved in the Hall-Heroult process by Raman spectroscopy
Malherbe, Cédric ULg; Gilbert, Bernard ULg

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 ▲]

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See detailGold-loaded carbon nanoparticles from poly(vinyl alcohol)-b-poly(acrylonitrile) non-shell-cross-linked micelles
Bryaskova, Rayna; Willet, Nicolas ULg; Duwez, Anne-Sophie ULg et al

in Chemistry : An Asian Journal (2009), 4(8), 1338-1345

Herein we show that a new amphiphilic poly(vinyl alcohol)-b-poly(acrylonitrile) block copolymer dispersed in water can be easily loaded with gold nanoparticles by addition of chlorauric acid followed by ... [more ▼]

Herein we show that a new amphiphilic poly(vinyl alcohol)-b-poly(acrylonitrile) block copolymer dispersed in water can be easily loaded with gold nanoparticles by addition of chlorauric acid followed by reduction by sodium borohydride. After deposition of the so-loaded micelles onto a silicon wafer, followed by an appropriate thermal treatment, the poly(acrylonitrile) core of the micelles is carbonized, while the poly(vinyl alcohol) shell is completely decomposed and volatilized, leading to gold encapsulated in carbon nanoparticles. The morphology of the micelles is maintained during thermal treatment without requiring shell-cross-linking of the micelles prior to pyrolysis. [less ▲]

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See detailAcidity in Ionic liquids: from the determination of an acidity scale to the application in catalytic reactions
Olivier-Bourbigou, Hélène; Gilbert, Bernard ULg; Magna, Lionel et al

Conference (2009)

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See detailTentative determination of the acidity level in room temperature ionic liquids by electrochemical methods
Malherbe, Cédric ULg; Robert, Thierry ULg; Magna, Lionel et al

in 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 ▲]

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See detailAbout the Acidity-Catalytic Activity Relationship in Ionic Liquids: Application to the Selective Isobutene Dimerization
Magna, Lionel; Bildé, Jean; Olivier-Bourbigou, Hélène et al

in Oil & Gas Science and Technology (2009), 64(6), 669

The Brønsted acidity level was evaluated for ionic liquids to which a strong acid has been added. As a first approach, the evaluation method was based on the determination of the Hammett acidity functions ... [more ▼]

The Brønsted acidity level was evaluated for ionic liquids to which a strong acid has been added. As a first approach, the evaluation method was based on the determination of the Hammett acidity functions H0, using UV-Visible spectroscopy. The acidity of protons is mainly determined by their solvation state and consequently, the properties of protons depend on both the nature of the solvent and the nature and concentration of the acid. An apparent acidity scale was defined following this principle. It was found that, for the investigated ionic liquids, the cation does not play a dominant role on the acidity level ([BMIm] ~ [BHIm] ~ [HNEt3]), whereas changing the nature of the anion of the ionic liquid may lead to very different acidities ([SbF6] > [PF6] > [BF4] > [NTf2] > [OTf]). This “acidity scale” was tentatively compared with an “activity scale” obtained for the dimerization of isobutene into isooctenes. The tendencies concerning the cation effect were confirmed ([BMIm] ~ [BuMePyrr] ~ [HNEt3]). The anion effect in only partially validated with a different behaviour for NTf2 type ionic liquids ([NTf2] ~ [SbF6] > [PF6] ~ [BF4] > [OTf]). By an adequate choice of the ionic liquid, selectivity for isobutene dimers can reach 88 wt% (at 70% isobutene conversion) with possible recycling of the catalytic system without loss of activity and selectivity. [less ▲]

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See detailA Comparison of the Acidity Levels in Room-Temperature Ionic Liquids
Robert, Thierry ULg; Magna, Lionel; Olivier-Bourbigou, Hélène et al

in Journal of the Electrochemical Society (2009), 156(9), 115

The Broensted acidity level was evaluated for several ionic liqs. ([BMIm][BF4], [BMIm][PF6], [BMIm][SbF6], [BMIm][OTf], [BMIm][NTf2], [HNET3][NTf2], and [HBIm][NTf2]) to which a strong acid, such as HNTf2 ... [more ▼]

The Broensted acidity level was evaluated for several ionic liqs. ([BMIm][BF4], [BMIm][PF6], [BMIm][SbF6], [BMIm][OTf], [BMIm][NTf2], [HNET3][NTf2], and [HBIm][NTf2]) to which a strong acid, such as HNTf2 [NTf2=N(CF3SO2)2] and HOTf (OTf=CF3SO3), has been added. The main purpose is to tentatively measure the influence on the resulting acidity of (i) the solvent anion or cation structure and (ii) the added acid nature. The evaluation method is based on the detn. of the Hammett acidity functions H0 using UV/visible spectroscopy. The acidity of protons is mainly detd. by their solvation state, and consequently, the properties of protons depend on both the nature of the solvent and the nature and concn. of the acid. In practice, for the investigated ionic liqs., the cation as well as the added acid nature does not play a dominant role, whereas changing the anion nature may lead to very different acidities. Indeed, for a similar content of added acid, the measured acidity levels are in the order PF6- > BF4- > NTf2- > OTf-. The problems of the influence of impurities on the final acidity and of the dissocg. character of the ionic liq. are addressed. [less ▲]

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See detailIn search of blood – detection of minute particles using spectroscopic methods
Lepot, Laurent ULg; Gilbert, Bernard ULg; De Wael, Kris et al

in Forensic Science International (2008), 180(1), 37-42

An examination protocol for rapid detection of remnants of blood particles on garments of suspects in bloody murder cases is described. Micro particles of blood are sampled along with fibres and hairs ... [more ▼]

An examination protocol for rapid detection of remnants of blood particles on garments of suspects in bloody murder cases is described. Micro particles of blood are sampled along with fibres and hairs using the tape lifting method. The tapings are searched with a low power microscope for red particles with morphology similar to blood. Presumed blood traces are further examined using microspectrophotometry on the cut out piece of taping. The typical visible spectrum of haemoglobin is characteristic for blood. Alternatively Raman spectroscopy can be used to measure the characteristic vibrational spectrum of haemoglobin. At a later stage, these particles may be removed from the piece of taping in order to extract the blood and attempt to obtain a genetic profile. [less ▲]

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See detailApplication of Raman spectroscopy to forensic fibre cases
Lepot, Laurent ULg; Gilbert, Bernard ULg; De Wael, Kris et al

in Science & Justice : Journal of the Forensic Science Society (2008), 48(3), 109-117

Five forensic fibre cases in which Raman spectroscopy proved to be a good confirmatory method for microspectrophotometry (MSP) are described. Absorption spectra in the visible range are indeed sometimes ... [more ▼]

Five forensic fibre cases in which Raman spectroscopy proved to be a good confirmatory method for microspectrophotometry (MSP) are described. Absorption spectra in the visible range are indeed sometimes characteristic of a certain dye but this one can be subsequently identified unambiguously by Raman spectroscopy using a spectral library. In other cases the comparison of Raman spectra of reference fibres and suspect fibres led to an improvement of the discrimination power. The Raman measurements have been performed directly on mounted fibres and the spectra showed only little interference from the mounting resin and glass. Raman spectroscopy is therefore a powerful method that can be applied in routine fibre analysis following optical microscopy and MSP measurements. [less ▲]

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See detailA propos des peintures romanes de la cathédrale de Tournai
Lepot, Laurent ULg; Gilbert, Bernard ULg; Denoël, Sophie

in Denoël, Sophie (Ed.) Les peintures murales, Les techniques : Actes du colloque (2008)

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See detailMaya blue-green pigments found in Calakmul, Mexico: a study by Raman and UV-visible spectroscopy
Moreno, Renata Garcia; Strivay, David ULg; Gilbert, Bernard ULg

in Journal Of Raman Spectroscopy (2008), 39(8), 1050-1056

After more than two decades of fieldwork in the Maya archaeological site of Calakmul, Mexico, numerous remnants of blue and green pigments have been reported on wall paintings, as well as on funerary ... [more ▼]

After more than two decades of fieldwork in the Maya archaeological site of Calakmul, Mexico, numerous remnants of blue and green pigments have been reported on wall paintings, as well as on funerary paraphernalia, such as masks, miniatures and vases. The importance of these pigments is linked to the sacred values that Maya people associate with blue and green colours since pre-Columbian times. These hues symbolise water, and are therefore associated with fertility and regeneration. This paper aims to perform a survey of the blue and green pigments used in the Early Classic and Late Classic periods in Calakmul (300-850 A.D.), in order to have a better understanding of their chemical composition and origin. Analyses were performed on microsamples using Raman and UV-visible spectroscopies to evaluate the possibilities that these techniques can offer in future in situ researches on Mesoamerican archaeological materials and objects. With these analyses, we have documented a large blue-green chromatic palette, which includes the earliest Blue Maya and Green Maya known to date, as well as malachite, pseudomalachite and an unknown-up-to-now blue-green mineral pigment, veszelyite, used specifically for ritual objects. The results indicate a careful selection of imported products and the mastering of a complex ancient Maya pictorial tradition. Copyright (c) 2008 John Wiley & Sons, Ltd. [less ▲]

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