Template-assisted crystallization of sulfates onto calcite: Implications for the prevention of salt damage

In situ X-ray diffraction (XRD) and environmental scanning electron microscope (ESEM) crystallization experiments show oriented growth of magnesium sulfate crystals on a diethylenetriamine-penta-methylene phosphonic acid (DTPMP) template adsorbed onto Iceland spar (calcite, CaCO3) cleavage surfaces....

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Main Authors: Ruiz-Agudo, E., Putnis, Christine, Pel, L., Rodriguez-Navarro, C.
Format: Journal Article
Published: 2013
Online Access:http://hdl.handle.net/20.500.11937/9143
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author Ruiz-Agudo, E.
Putnis, Christine
Pel, L.
Rodriguez-Navarro, C.
author_facet Ruiz-Agudo, E.
Putnis, Christine
Pel, L.
Rodriguez-Navarro, C.
author_sort Ruiz-Agudo, E.
building Curtin Institutional Repository
collection Online Access
description In situ X-ray diffraction (XRD) and environmental scanning electron microscope (ESEM) crystallization experiments show oriented growth of magnesium sulfate crystals on a diethylenetriamine-penta-methylene phosphonic acid (DTPMP) template adsorbed onto Iceland spar (calcite, CaCO3) cleavage surfaces. Epsomite (MgSO4·7H2O) and hexahydrite (MgSO4·6H2O) crystallize (depending on the ambient conditions) in the presence of DTPMP with (010)epsomite// (101Ì...4)calcite and (1Ì...11)hexahydrite// (101Ì...4)calcite, whereas in the absence of DTPMP they show no preferred orientation. On the other hand, sodium sulfate (mirabilite, Na 2SO4·10H2O) nucleates onto a Ca-DTPMP precipitate with (001)mirabilite//(101Ì...4) calcite. In contrast, different sodium sulfate phases crystallize and grow with no preferred crystallographic orientation in the absence of an organic additive. These results allow us to propose a model for the interaction calcite-DTPMP-Na and Mg sulfates based on the template-assisted nucleation and oriented heterogeneous crystallization, mediated by a Ca-precipitate, of inorganic salts on calcitic substrates. This effect results in a (measured) reduction in the critical supersaturation reached by these salts when crystallizing in confined geometries, i.e., a pore, thus resulting in a reduction in crystallization pressure and damage to porous substrates such as building stones. These results have implications in fields where in-pore crystallization of salts results in damage or plugging of the porous network, e.g., cultural heritage conservation and in the oil industry, where phosphonates are used as crystallization inhibitors. © 2012 American Chemical Society.
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spelling curtin-20.500.11937-91432018-03-29T09:05:56Z Template-assisted crystallization of sulfates onto calcite: Implications for the prevention of salt damage Ruiz-Agudo, E. Putnis, Christine Pel, L. Rodriguez-Navarro, C. In situ X-ray diffraction (XRD) and environmental scanning electron microscope (ESEM) crystallization experiments show oriented growth of magnesium sulfate crystals on a diethylenetriamine-penta-methylene phosphonic acid (DTPMP) template adsorbed onto Iceland spar (calcite, CaCO3) cleavage surfaces. Epsomite (MgSO4·7H2O) and hexahydrite (MgSO4·6H2O) crystallize (depending on the ambient conditions) in the presence of DTPMP with (010)epsomite// (101Ì...4)calcite and (1Ì...11)hexahydrite// (101Ì...4)calcite, whereas in the absence of DTPMP they show no preferred orientation. On the other hand, sodium sulfate (mirabilite, Na 2SO4·10H2O) nucleates onto a Ca-DTPMP precipitate with (001)mirabilite//(101Ì...4) calcite. In contrast, different sodium sulfate phases crystallize and grow with no preferred crystallographic orientation in the absence of an organic additive. These results allow us to propose a model for the interaction calcite-DTPMP-Na and Mg sulfates based on the template-assisted nucleation and oriented heterogeneous crystallization, mediated by a Ca-precipitate, of inorganic salts on calcitic substrates. This effect results in a (measured) reduction in the critical supersaturation reached by these salts when crystallizing in confined geometries, i.e., a pore, thus resulting in a reduction in crystallization pressure and damage to porous substrates such as building stones. These results have implications in fields where in-pore crystallization of salts results in damage or plugging of the porous network, e.g., cultural heritage conservation and in the oil industry, where phosphonates are used as crystallization inhibitors. © 2012 American Chemical Society. 2013 Journal Article http://hdl.handle.net/20.500.11937/9143 10.1021/cg300744x restricted
spellingShingle Ruiz-Agudo, E.
Putnis, Christine
Pel, L.
Rodriguez-Navarro, C.
Template-assisted crystallization of sulfates onto calcite: Implications for the prevention of salt damage
title Template-assisted crystallization of sulfates onto calcite: Implications for the prevention of salt damage
title_full Template-assisted crystallization of sulfates onto calcite: Implications for the prevention of salt damage
title_fullStr Template-assisted crystallization of sulfates onto calcite: Implications for the prevention of salt damage
title_full_unstemmed Template-assisted crystallization of sulfates onto calcite: Implications for the prevention of salt damage
title_short Template-assisted crystallization of sulfates onto calcite: Implications for the prevention of salt damage
title_sort template-assisted crystallization of sulfates onto calcite: implications for the prevention of salt damage
url http://hdl.handle.net/20.500.11937/9143