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- Golets, M., et al.
(author)
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Understanding the thermal decomposition mechanism of a halogen-free chelated orthoborate-based ionic liquid : a combined computational and experimental study
- 2016
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In: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 18, s. 22458-22466
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Journal article (peer-reviewed)abstract
- 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.
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| 3. |
- Trublet, Mylene
(author)
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Titanium(IV) Phosphates : The Next Generation of Wastewater Sorbents
- 2018
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Doctoral thesis (other academic/artistic)abstract
- Treatment of industrial waters containing heavy metal ions is essential before being discharged into the environment. Consequently, European regulations have been established to control and limit the amount of heavy metals released. There is a need to develop efficient water treatment techniques that can remove contaminants with respect to these EU regulations.Ion-exchange is one of the processes that is being investigated due to fast kinetics, high treatment capacity and its ability to remove heavy metal ions present in trace amounts. Titanium phosphates (TiP) are a group of inorganic ion-exchangers that have demonstrated to be particularly selective towards transition metal ions in aqueous solutions. Two types of ion-exchange units are present in TiP material, which are –HPO4 and –H2PO4 groups. Their structural characteristic is highly dependent on the synthesis conditions, which include the source of titanium, temperature, reaction time and P2O5:TiO2 ratio. Most of the studies have been performed on amorphous TiP containing a mixture of both exchange units, with –HPO4 groups being predominant; as crystalline TiP and –H2PO4 based TiP are often obtained in difficult conditions, high temperature (up to 250 °C) and/or long reaction time (up to 30 days) and/or using autoclave. Despite promising properties depicted in batch conditions, very few data in continuous flow systems (fixed-bed columns) have been reported.In this work, amorphous TiP composed of entirely –H2PO4 ion-exchange units (TiP1) was synthesized at mild conditions using a TiOSO4 solution and HCl/deionized water as post-synthesis treatments. The sorbent was characterized using a range of techniques (solid-state 31P MAS NMR, Raman, XRD, TGA, BET, Elemental analysis, EXAFS and XANES,) and tested in batch and column set-ups towards single and multi-component waters. The chemical formula of TiP1 was established as TiO(OH)(H2PO4)·H2O and it was found that the synthesis of TiP1 was also dependent on the TiO2/H2SO4 content in the primary titanium solution.The material displayed a high maximum exchange capacity of ca. 6.4 meq.g-1, expressed as the sodium uptake. The actual ion-exchange capacity towards divalent metal ions was calculated to be ca. 3.4 meq.g-1 in batch condition and up to 4.1 meq.g-1 in fixed-bed column, which is to date the highest recorded for TiP materials. Kinetics of the exchange processes have been studied and the equilibrium was reached within 5-20 minutes. Modeling of the breakthrough curves was achieved using the Thomas model, indicating that the rate driving forces of the processes follow second-order reversible kinetics. The TiP1 sorbent has shown to maintain a high selectivity towards heavy metal ions in multi-component systems (including closed-mine waters) when column studies were performed. The sorption behavior of TiP1 in batch experiments correlates very well with data obtained in fixed-bed column conditions, confirming that prediction of the sorption behavior on the basis of batch data is conceivable.Another important aspect of this work also involves the mild syntheses of crystalline α-TiP, Ti(HPO4)·H2O, and LTP (Linked Titanium Phosphate) composed of α-TiP and TiP1, where the structural characteristics of these materials were investigated using solid-state NMR, XRD, TGA, EXAFS and XANES.
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| 5. |
- Farzaneh, Amirfarrokh, et al.
(author)
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Adsorption of Butanol and Water Vapors in Silicalite‑1 Films with a Low Defect Density
- 2016
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In: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 32, s. 11789-11798
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Journal article (peer-reviewed)abstract
- 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.
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| 8. |
- Johansson, Karin, et al.
(author)
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Kinetics of the hydration reactions in the cement paste with mechanochemically modified cement 29Si magic-angle-spinning NMR study
- 1999
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In: Cement and Concrete Research. - 0008-8846 .- 1873-3948. ; 29:10, s. 1575-1581
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Journal article (peer-reviewed)abstract
- A comparative 29Si solid state NMR study of kinetics of the hydration reactions in cement pastes based on rapid-hardening ordinary Portland cement (SH) and on the mechanochemically modified cement (MSH) is presented. The mechanical activation of a cement/silica fume blend in a vibrating mill accelerates the hydration reactions by 15-20%, especially during the initial period of hardening. Variations in relative intensities of 29Si resonances assigned to the hydration products in SH/MSH blends suggest different structures of hydrated SH nets. This can be correlated with a pronounced increase of the MSH-cement binding capacity reported earlier.
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| 10. |
- Wang, Zhou, et al.
(author)
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Temperature-dependent changes of physicochemical and tribological properties of acrylonitrile-butadiene rubber elastomer upon ageing in hexadecane and diethylene glycol dibutyl ether
- 2013
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In: Proceedings of the Institution of mechanical engineers. Part J, journal of engineering tribology. - : SAGE Publications. - 1350-6501 .- 2041-305X. ; 227:8, s. 826-836
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Journal article (peer-reviewed)abstract
- Acrylonitrile-butadiene rubber elastomers are widely used in seal and tire industries. Physiochemical, surface and tribological properties of acrylonitrile-butadiene rubber exposed to a lubricant in a sealed mechanical contact may gradually change, in particular, at elevated temperatures. In this study, industrial-grade acrylonitrile-butadiene rubber elastomers were aged in two model non-additivated base oils, namely non-polar hexadecane and polar diethylene glycol dibutyl ether at both ambient (298 K) and elevated (398 K) temperatures from 1 to 168 h. Mass changes of acrylonitrile-butadiene rubber before and after ageing indicated that acrylonitrile-butadiene rubber had distinct ageing dynamics in different model base oils and at different temperatures. For acrylonitrile-butadiene rubber aged in nonpolar hexadecane, the rate of weight loss of the rubber was larger at 398 K compared to that at 298 K. On the contrary, distinct weight-gaining (swelling) dynamics were observed for acrylonitrile-butadiene rubber aged in polar diethylene glycol dibutyl ether at 298 and 398 K. Based on Fourier transform infrared spectroscopy, liquid and solid-state nuclear magnetic resonance spectroscopy and energy dispersive spectroscopy analyses, it was found that aldehydes and sulfur- and zinc-containing compounds were leached out from acrylonitrile-butadiene rubber aged in both hexadecane and diethylene glycol dibutyl ether. The results of tribological studies showed that the non-aged acrylonitrile-butadiene rubber has a good wear-resistance. Acrylonitrile-butadiene rubber samples had a very similar surface topography before and after tribo-tests. However, the worn surfaces of acrylonitrile-butadiene rubber samples were characterized by fine scoring (abrasion) marks after ageing in both model base oils. This has been attributed to changes in the steel–rubber contact environment during the sliding process and degradation of mechanical properties of acrylonitrile-butadiene rubber after ageing. For one acrylonitrile-butadiene rubber sample (after ageing in hexadecane at 398 K), very stable friction in the steel–rubber contact was observed.
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