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Calcite Surfaces Modified with Carboxylic Acids (C(2) to C(18)): Layer Organization, Wettability, Stability, and Molecular Structural Properties

[Image: see text] A fundamental understanding of the interactions between mineral surfaces and amphiphilic surface modification agents is needed for better control over the production and uses of mineral fillers. Here, we controlled the carboxylic acid layer formation conditions on calcite surfaces...

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Autores principales: Wojas, Natalia A., Tyrode, Eric, Corkery, Robert, Ernstsson, Marie, Wallqvist, Viveca, Järn, Mikael, Swerin, Agne, Schoelkopf, Joachim, Gane, Patrick A. C., Claesson, Per M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10601537/
https://www.ncbi.nlm.nih.gov/pubmed/37824837
http://dx.doi.org/10.1021/acs.langmuir.3c01252
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author Wojas, Natalia A.
Tyrode, Eric
Corkery, Robert
Ernstsson, Marie
Wallqvist, Viveca
Järn, Mikael
Swerin, Agne
Schoelkopf, Joachim
Gane, Patrick A. C.
Claesson, Per M.
author_facet Wojas, Natalia A.
Tyrode, Eric
Corkery, Robert
Ernstsson, Marie
Wallqvist, Viveca
Järn, Mikael
Swerin, Agne
Schoelkopf, Joachim
Gane, Patrick A. C.
Claesson, Per M.
author_sort Wojas, Natalia A.
collection PubMed
description [Image: see text] A fundamental understanding of the interactions between mineral surfaces and amphiphilic surface modification agents is needed for better control over the production and uses of mineral fillers. Here, we controlled the carboxylic acid layer formation conditions on calcite surfaces with high precision via vapor deposition. The properties of the resulting carboxylic acid layers were analyzed using surface-sensitive techniques, such as atomic force microscopy (AFM), contact angle measurements, angle resolved X-ray photoelectron spectroscopy (XPS), and vibrational sum-frequency spectroscopy. A low wettability was achieved with long hydrocarbon chain carboxylic acids such as stearic acid. The stearic acid layer formed by vapor deposition is initially patchy, but with increasing vapor exposure time, the patches grow and condense into a homogeneous layer with a thickness close to that expected for a monolayer as evaluated by AFM and XPS. The build-up process of the layer occurs more rapidly at higher temperatures due to the higher vapor pressure. The stability of the deposited fatty acid layer in the presence of a water droplet increases with the chain length and packing density in the adsorbed layer. Vibrational sum frequency spectroscopy data demonstrate that the stearic acid monolayers on calcite have their alkyl chains in an all-trans conformation and are anisotropically distributed on the plane of the surface, forming epitaxial monolayers. Vibrational spectra also show that the stearic acid molecules interact with the calcite surface through the carboxylic acid headgroup in both its protonated and deprotonated forms. The results presented provide new molecular insights into the properties of adsorbed carboxylic acid layers on calcite.
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spelling pubmed-106015372023-10-27 Calcite Surfaces Modified with Carboxylic Acids (C(2) to C(18)): Layer Organization, Wettability, Stability, and Molecular Structural Properties Wojas, Natalia A. Tyrode, Eric Corkery, Robert Ernstsson, Marie Wallqvist, Viveca Järn, Mikael Swerin, Agne Schoelkopf, Joachim Gane, Patrick A. C. Claesson, Per M. Langmuir [Image: see text] A fundamental understanding of the interactions between mineral surfaces and amphiphilic surface modification agents is needed for better control over the production and uses of mineral fillers. Here, we controlled the carboxylic acid layer formation conditions on calcite surfaces with high precision via vapor deposition. The properties of the resulting carboxylic acid layers were analyzed using surface-sensitive techniques, such as atomic force microscopy (AFM), contact angle measurements, angle resolved X-ray photoelectron spectroscopy (XPS), and vibrational sum-frequency spectroscopy. A low wettability was achieved with long hydrocarbon chain carboxylic acids such as stearic acid. The stearic acid layer formed by vapor deposition is initially patchy, but with increasing vapor exposure time, the patches grow and condense into a homogeneous layer with a thickness close to that expected for a monolayer as evaluated by AFM and XPS. The build-up process of the layer occurs more rapidly at higher temperatures due to the higher vapor pressure. The stability of the deposited fatty acid layer in the presence of a water droplet increases with the chain length and packing density in the adsorbed layer. Vibrational sum frequency spectroscopy data demonstrate that the stearic acid monolayers on calcite have their alkyl chains in an all-trans conformation and are anisotropically distributed on the plane of the surface, forming epitaxial monolayers. Vibrational spectra also show that the stearic acid molecules interact with the calcite surface through the carboxylic acid headgroup in both its protonated and deprotonated forms. The results presented provide new molecular insights into the properties of adsorbed carboxylic acid layers on calcite. American Chemical Society 2023-10-12 /pmc/articles/PMC10601537/ /pubmed/37824837 http://dx.doi.org/10.1021/acs.langmuir.3c01252 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Wojas, Natalia A.
Tyrode, Eric
Corkery, Robert
Ernstsson, Marie
Wallqvist, Viveca
Järn, Mikael
Swerin, Agne
Schoelkopf, Joachim
Gane, Patrick A. C.
Claesson, Per M.
Calcite Surfaces Modified with Carboxylic Acids (C(2) to C(18)): Layer Organization, Wettability, Stability, and Molecular Structural Properties
title Calcite Surfaces Modified with Carboxylic Acids (C(2) to C(18)): Layer Organization, Wettability, Stability, and Molecular Structural Properties
title_full Calcite Surfaces Modified with Carboxylic Acids (C(2) to C(18)): Layer Organization, Wettability, Stability, and Molecular Structural Properties
title_fullStr Calcite Surfaces Modified with Carboxylic Acids (C(2) to C(18)): Layer Organization, Wettability, Stability, and Molecular Structural Properties
title_full_unstemmed Calcite Surfaces Modified with Carboxylic Acids (C(2) to C(18)): Layer Organization, Wettability, Stability, and Molecular Structural Properties
title_short Calcite Surfaces Modified with Carboxylic Acids (C(2) to C(18)): Layer Organization, Wettability, Stability, and Molecular Structural Properties
title_sort calcite surfaces modified with carboxylic acids (c(2) to c(18)): layer organization, wettability, stability, and molecular structural properties
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10601537/
https://www.ncbi.nlm.nih.gov/pubmed/37824837
http://dx.doi.org/10.1021/acs.langmuir.3c01252
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