Characterization of Monochromate and Hemichromate AFm Phases and Chromate-Containing Ettringite by¹H,²⁷Al, and⁵³Cr MAS NMR Spectroscopy

TY - JOUR

T1 - Characterization of Monochromate and Hemichromate AFm Phases and Chromate-Containing Ettringite by1H,27Al, and53Cr MAS NMR Spectroscopy

AU - Nie, Shuai

AU - Skibsted, Jørgen

N1 - Publisher Copyright: © 2022 by the authors. Licensee MDPI, Basel, Switzerland.

PY - 2022/3

Y1 - 2022/3

N2 - The calcium aluminate hydrate AFm and AFt phases formed upon hydration of Portland cement have an important role in the stabilization and solidification of hazardous chromate ions in hardened cement. AFm monochromate (Ca4[Al(OH)6]2(CrO4)12H2O), AFm hemichromate (Ca4[Al(OH)6]2(CrO4)0.5(OH)12H2O) and the chromate-containing AFt phase, Ca6[Al(OH)6]2- (CrO4)324H2O, were synthesized and investigated by1H,27Al, and53Cr MAS NMR spectroscopy.27Al quadrupolar coupling parameters (CQ, ηQ) and isotropic chemical shifts (δiso) were determined for the three phases, including two distinct Al sites in chromate-AFt, as observed by27Al MAS and MQMAS NMR. Two dominant peaks are apparent in the1H MAS NMR spectra of each of the phases. For the AFm phases, these resonances are assigned to framework hydroxyl groups (1.7–2.0 ppm) and water molecules/hydroxyls (5.0–5.5 ppm) in the interlayer. For chromate-AFt, the peaks are ascribed to framework hydroxyl groups in the [Ca6Al2(OH)12]6+ columns (~1.4 ppm) and water molecules (~4.8 ppm) associated with the Ca ions.53Cr MAS NMR spectra acquired at 22.3 T for the samples show a narrow resonance for both chromate AFm phases, whereas indications of three distinct Cr resonances are apparent for the chromate AFt. The absence of any second-order quadrupolar effects in the53Cr NMR spectra strongly suggests that the chromate ions are highly mobile in the anionic sites of the AFm and AFt structures. The NMR data reported in this work are in agreement with the reported crystal structures for the chromate AFm and AFt phases and may be useful for identification and characterization of chromate fixation in cementitious systems, complementing information gained from conventional powder X-ray diffraction studies.

AB - The calcium aluminate hydrate AFm and AFt phases formed upon hydration of Portland cement have an important role in the stabilization and solidification of hazardous chromate ions in hardened cement. AFm monochromate (Ca4[Al(OH)6]2(CrO4)12H2O), AFm hemichromate (Ca4[Al(OH)6]2(CrO4)0.5(OH)12H2O) and the chromate-containing AFt phase, Ca6[Al(OH)6]2- (CrO4)324H2O, were synthesized and investigated by1H,27Al, and53Cr MAS NMR spectroscopy.27Al quadrupolar coupling parameters (CQ, ηQ) and isotropic chemical shifts (δiso) were determined for the three phases, including two distinct Al sites in chromate-AFt, as observed by27Al MAS and MQMAS NMR. Two dominant peaks are apparent in the1H MAS NMR spectra of each of the phases. For the AFm phases, these resonances are assigned to framework hydroxyl groups (1.7–2.0 ppm) and water molecules/hydroxyls (5.0–5.5 ppm) in the interlayer. For chromate-AFt, the peaks are ascribed to framework hydroxyl groups in the [Ca6Al2(OH)12]6+ columns (~1.4 ppm) and water molecules (~4.8 ppm) associated with the Ca ions.53Cr MAS NMR spectra acquired at 22.3 T for the samples show a narrow resonance for both chromate AFm phases, whereas indications of three distinct Cr resonances are apparent for the chromate AFt. The absence of any second-order quadrupolar effects in the53Cr NMR spectra strongly suggests that the chromate ions are highly mobile in the anionic sites of the AFm and AFt structures. The NMR data reported in this work are in agreement with the reported crystal structures for the chromate AFm and AFt phases and may be useful for identification and characterization of chromate fixation in cementitious systems, complementing information gained from conventional powder X-ray diffraction studies.

KW - H NMR

KW - Al NMR

KW - Cr NMR

KW - Calcium aluminate hydrates

KW - Chromate ions

UR - http://www.scopus.com/inward/record.url?scp=85129231763&partnerID=8YFLogxK

U2 - 10.3390/min12030371

DO - 10.3390/min12030371

M3 - Journal article

AN - SCOPUS:85129231763

SN - 2075-163X

VL - 12

JO - Minerals

JF - Minerals

IS - 3

M1 - 371

ER -