Reactions of Polyphosphoric Acid and Bitumen Model Compounds with Oxygenated Functional Groups: Where Is the Phosphorylation?

Masson, J-F.; Gagne, M.; Robertson, Gilles P.; Collins, Peter

doi:10.1021/ef800511v

Cited by 24 publications

(17 citation statements)

References 12 publications

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“…It could be possibly from ketone groups. [26][27][28] There is no 13 C peak near 175 ppm which comes from a carboxyl (-COOH) group. [29][30][31] Since carboxyl groups have hydrogen, its 13 C peak must be cross-polarized if the groups are really present in the sample.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

The Structure of Graphite Oxide: Investigation of Its Surface Chemical Groups

Lee¹,

Seo²,

Felix³

et al. 2010

J. Phys. Chem. B

358

249

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The structure of graphite oxide (GO) has been systematically studied using various tools such as SEM, TEM, XRD, Fourier transform infrared spectroscopy (FT-IR), X-ray photoemission spectroscopy (XPS), (13)C solid-state NMR, and O K-edge X-ray absorption near edge structure (XANES). The TEM data reveal that GO consists of amorphous and crystalline phases. The XPS data show that some carbon atoms have sp(3) orbitals and others have sp(2) orbitals. The ratio of sp(2) to sp(3) bonded carbon atoms decreases as sample preparation times increase. The (13)C solid-state NMR spectra of GO indicate the existence of -OH and -O- groups for which peaks appear at 60 and 70 ppm, respectively. FT-IR results corroborate these findings. The existence of ketone groups is also implied by FT-IR, which is verified by O K-edge XANES and (13)C solid-state NMR. We propose a new model for GO based on the results; -O-, -OH, and -C=O groups are on the surface.

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Section: Resultsmentioning

confidence: 99%

“…The broad peak at 195 ppm does not cross-polarize. It could be possibly from ketone groups [26][27][28]. There is no 13 C peak near 175 ppm which comes from carboxyl (-COOH) group [29][30][31].…”

Section: Resultsmentioning

confidence: 99%

The Structure of Graphite Oxide: Investigation of Its Surface Chemical Groups

Lee¹,

Seo²,

Felix³

et al. 2010

J. Phys. Chem. B

358

249

View full text Add to dashboard Cite

show abstract

“…They all present, in the wavenumber interval scanned, three well-defined bands: the first, in the region 1760-1665 cm -1 due to the stretching vibration of the carbonyl (C=O) bond, and the second and third peaks, in the regions 1470-1350 and 1390-1370 cm -1 due to the bending vibration of the CH2&CH3 bonds and bending vibration of the CH3 bond, respectively [22]. However, only the "PG-H2SO4-150" sample displays a new absorption band, from 1060 to 1180 cm -1 , related to C−O−P vibrations [23]. Therefore, FTIR results provide evidences of the existence of chemical reactions involving phosphorus contained in the PG fraction which is not CaSO4 (about 8 wt.%), and which seem to be the responsible for the viscosity increase observed in Figure 1.…”

Section: Modification and Microstructurementioning

confidence: 99%

Valorization of phosphogypsum waste as asphaltic bitumen modifier

Cuadri

Navarro

García‐Morales

et al. 2014

Journal of Hazardous Materials

116

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The accumulation of phosphogypsum wastes from the fertilizer industries, which remain in regulated stacks occupying considerable land resources, is causing significant environment problems worldwide. In that sense, the scientific community is being pressured to find alternative ways for their disposal. In this research, we propose a novel application for phosphogypsum wastes, as a modifier of bitumen for flexible road pavements. Viscous flow tests carried out on bitumen modified with a phosphogypsum waste and doped with sulfuric acid demonstrated an extraordinary increase in viscosity, at 60 ºC, when compared to a counterpart sample which had been modified with gypsum, the main component of phosphogypsum. Similarly, a significant improvement in the viscoelastic response of the resulting material at high temperatures was also found. FTIR (Fourier transform infrared spectroscopy) scans provided evidences of the existence of chemical reactions involving phosphorus, as revealed by a new absorption band from 1060 to 1180 cm -1 , related to C−O−P vibrations. This result points at phosphorus contained in the phosphogypsum impurities to be the actual "modifying" substance. Furthermore, no C-O-P band was observed in the absence of sulfuric acid, which seems to be the "promoting" agent of this type of bond.

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“…Using isolated model compounds containing oxygen functional groups (representative compounds for phenol, ether, ketone, and carboxylic acid), Masson et al concluded that phenols or aromatic carboxylic acids are not phosphorylated, indicating that phosphate esters cannot be responsible for the stiffening effect of PPA. 17 In two samples of PPA-modified bitumen derived from different sources of crude, Baumgardner et al observed a significant increase in asphaltene content (nheptane insolubles) with a reduced molecular weight, a decrease in resin content, and a nonmonotonous trend in the content of saturates; they proposed several possible underlying stiffening mechanisms such as the formation of PPA adducts, the alkylation of aromatics, and the formation of ionic clusters. 14 More or less, similar reports have documented the increase in asphaltene content and the decrease in resins/aromatics after PPA modification.…”

Section: ■ Introductionmentioning

confidence: 99%

“…However, the mechanism underlying the specific interactions between PPA and SARA fractions that lead to the prominent features for PPA-modified bitumen is still elusive. Considering the inherent complexity of bitumen and the many unknowns in the interplay between PPA and a sea of bituminous molecular compounds, almost all we know about the molecular mechanism underlying the PPA interactions is limited to the studies performed on model compounds; data using 1 H NMR, 31 P NMR, and FTIR techniques is scarce. ,− On this basis, Giavarini et al and Orange et al suggested the phosphorylation of asphaltenes for increasing the amount of n -heptane precipitates. Using isolated model compounds containing oxygen functional groups (representative compounds for phenol, ether, ketone, and carboxylic acid), Masson et al concluded that phenols or aromatic carboxylic acids are not phosphorylated, indicating that phosphate esters cannot be responsible for the stiffening effect of PPA .…”

Section: Introductionmentioning

confidence: 99%

Moderating Effects of Paraffin Wax on Interactions between Polyphosphoric Acid and Bitumen Constituents

Mousavi

Fini

2019

ACS Sustainable Chem. Eng.

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Despite the merits of using polyphosphoric acid (PPA) in modification of bitumen, its desirable stiffening effect on bitumen is totally composition-dependent. While asphaltenes and resins are correctly introduced as the immediate components affected by PPA, our laboratory rheological investigations show that bitumen's wax content could be a potential interference for PPA's modification function. As evidenced by the complex viscosity test, PPA is very effective in low-wax bitumen, but its effect on high-wax bitumen is quite negligible. In a high-wax medium, the trend of interaction energy improvement with the number of wax chains suggests that the crystalline networks of wax can interfere in interactions of PPA with either asphaltene or resin through concealing interaction sites of asphaltene and resin. This in turn leads to the reduction of their accessible active sites for interacting with PPA. To study the working mechanism of PPA on bitumen constituents, the density functional theory (DFT) approach and energy decomposition analysis (EDA) were performed on the pairs of PPA−asphaltene, PPA−resin, and PPA−wax molecules. In the case of the PPA−asphaltene interaction, EDA shows clear contributions of electrostatic, orbital, and dispersion forces. In the resin fraction, the strong interactions between basic sites of the resin molecules and PPA lead to the formation of ion-pair compounds stabilized through oppositely charged ions held together via Coulombic attraction. The formation of these new entities, which are often nonsoluble in heptane, can further explain the decrease of resin content after PPA modification. The reduction of resin is followed by an increase in the content of asphaltene with a smaller molecular weight in n-heptane precipitates, which is in line with our experiments and that of other researchers.

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Reactions of Polyphosphoric Acid and Bitumen Model Compounds with Oxygenated Functional Groups: Where Is the Phosphorylation?

Cited by 24 publications

References 12 publications

The Structure of Graphite Oxide: Investigation of Its Surface Chemical Groups

The Structure of Graphite Oxide: Investigation of Its Surface Chemical Groups

Valorization of phosphogypsum waste as asphaltic bitumen modifier

Moderating Effects of Paraffin Wax on Interactions between Polyphosphoric Acid and Bitumen Constituents

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