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Title: Unravelling the Chemical Influence of Water on the PMMA/Aluminum Oxide Hybrid Interface In Situ

Abstract

Understanding the stability of chemical interactions at the polymer/metal oxide interface under humid conditions is vital to understand the long-term durability of hybrid systems. Therefore, the interface of ultrathin PMMA films on native aluminum oxide, deposited by reactive adsorption, was studied. The characterization of the interface of the coated substrates was performed using ambient pressure X-ray photoelectron spectroscopy (APXPS), Fourier transform infrared spectroscopy in the Kretschmann geometry (ATR-FTIR Kretschmann) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The formation of hydrogen bonds and carboxylate ionic bonds at the interface are observed. The formed ionic bond is stable up to 5 Torr water vapour pressure as shown by APXPS. However, when the coated samples are exposed to an excess of aqueous electrolyte, an increase in the amount of carboxylate bonds at the interface, as a result of hydrolysis of the methoxy group, is observed by ATR-FTIR Kretschmann. In conclusion, these observations, supported by ToF-SIMS spectra, lead to the proposal of an adsorption mechanism of PMMA on aluminum oxide, which shows the formation of methanol at the interface and the effect of water molecules on the different interfacial interactions.

Authors:
ORCiD logo [1];  [2];  [3];  [4]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [3];  [3];  [2]; ORCiD logo [2]
  1. Vrije Univ. Brussel, Brussels, (Belgium). Dept. of Electrochemical and Surface Engineering (SURF); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. Vrije Univ. Brussel, Brussels, (Belgium). Dept. of Electrochemical and Surface Engineering (SURF)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  4. Delft Univ. of Technology (Netherlands). Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOD; Research Foundation Flanders (FWO)
OSTI Identifier:
1419452
Grant/Contract Number:
AC02-05CH11231; HDTRA11510005
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 7; Journal Issue: 1; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Pletincx, Sven, Marcoen, Kristof, Trotochaud, Lena, Fockaert, Laura-Lynn, Mol, Johannes M. C., Head, Ashley R., Karslioğlu, Osman, Bluhm, Hendrik, Terryn, Herman, and Hauffman, Tom. Unravelling the Chemical Influence of Water on the PMMA/Aluminum Oxide Hybrid Interface In Situ. United States: N. p., 2017. Web. doi:10.1038/s41598-017-13549-z.
Pletincx, Sven, Marcoen, Kristof, Trotochaud, Lena, Fockaert, Laura-Lynn, Mol, Johannes M. C., Head, Ashley R., Karslioğlu, Osman, Bluhm, Hendrik, Terryn, Herman, & Hauffman, Tom. Unravelling the Chemical Influence of Water on the PMMA/Aluminum Oxide Hybrid Interface In Situ. United States. doi:10.1038/s41598-017-13549-z.
Pletincx, Sven, Marcoen, Kristof, Trotochaud, Lena, Fockaert, Laura-Lynn, Mol, Johannes M. C., Head, Ashley R., Karslioğlu, Osman, Bluhm, Hendrik, Terryn, Herman, and Hauffman, Tom. 2017. "Unravelling the Chemical Influence of Water on the PMMA/Aluminum Oxide Hybrid Interface In Situ". United States. doi:10.1038/s41598-017-13549-z. https://www.osti.gov/servlets/purl/1419452.
@article{osti_1419452,
title = {Unravelling the Chemical Influence of Water on the PMMA/Aluminum Oxide Hybrid Interface In Situ},
author = {Pletincx, Sven and Marcoen, Kristof and Trotochaud, Lena and Fockaert, Laura-Lynn and Mol, Johannes M. C. and Head, Ashley R. and Karslioğlu, Osman and Bluhm, Hendrik and Terryn, Herman and Hauffman, Tom},
abstractNote = {Understanding the stability of chemical interactions at the polymer/metal oxide interface under humid conditions is vital to understand the long-term durability of hybrid systems. Therefore, the interface of ultrathin PMMA films on native aluminum oxide, deposited by reactive adsorption, was studied. The characterization of the interface of the coated substrates was performed using ambient pressure X-ray photoelectron spectroscopy (APXPS), Fourier transform infrared spectroscopy in the Kretschmann geometry (ATR-FTIR Kretschmann) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The formation of hydrogen bonds and carboxylate ionic bonds at the interface are observed. The formed ionic bond is stable up to 5 Torr water vapour pressure as shown by APXPS. However, when the coated samples are exposed to an excess of aqueous electrolyte, an increase in the amount of carboxylate bonds at the interface, as a result of hydrolysis of the methoxy group, is observed by ATR-FTIR Kretschmann. In conclusion, these observations, supported by ToF-SIMS spectra, lead to the proposal of an adsorption mechanism of PMMA on aluminum oxide, which shows the formation of methanol at the interface and the effect of water molecules on the different interfacial interactions.},
doi = {10.1038/s41598-017-13549-z},
journal = {Scientific Reports},
number = 1,
volume = 7,
place = {United States},
year = 2017,
month =
}

Journal Article:
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  • Probing initial interactions at the interface of hybrid systems under humid conditions has the potential to reveal the local chemical environment at solid/solid interfaces under real-world, technologically relevant conditions. Here in this paper, we show that ambient pressure X-ray photoelectron spectroscopy (APXPS) with a conventional X-ray source can be used to study the effects of water exposure on the interaction of a nanometer-thin polyacrylic acid (PAA) layer with a native aluminum oxide surface. The formation of a carboxylate ionic bond at the interface is characterized both with APXPS and in situ attenuated total reflectance Fourier transform infrared spectroscopy in themore » Kretschmann geometry (ATR-FTIR Kretschmann). When water is dosed in the APXPS chamber up to 5 Torr (~28% relative humidity), an increase in the amount of ionic bonds at the interface is observed. To confirm our APXPS interpretation, complementary ATR-FTIR Kretschmann experiments on a similar model system, which is exposed to an aqueous electrolyte, are conducted. These spectra demonstrate that water leads to an increased wet adhesion through increased ionic bond formation.« less
  • The fate of Pb in the environment is highly dependent on sorption and desorption reactions on solid surfaces. In this study Pb sorption and desorption kinetics on {gamma}-Al{sub 2}O{sub 3} at pH 6.50, I = 0.1 M, and [Pb]{sub initial} = 2 mM were investigated using both macroscopic and spectroscopic measurements. X-ray absorption fine structure (XAFS) spectroscopy revealed a Pb-Al bond distance of 3.40 {angstrom}, consistent with an inner-sphere bidentate bonding mechanism. XAFS results show no change with time in the average local atomic structure surrounding the Pb and no indication of the formation of Pb surface precipitates. Adsorption kineticsmore » were initially fast, resulting in 76% of the total sorption occurring within 15 min, followed by a slow continuous sorption reaction likely resulting from diffusion through micropores. Desorption at I = 0.1 M and pH 6.50 was studied using a cation-exchange resin as a sink for Pb(aq). Under these conditions, Pb desorption was 98% reversible within 3 days of incubation time. Furthermore, desorption and adsorption kinetics demonstrated similar trends: a fast reaction followed by a slow reaction. The use of spectroscopy combined with adsorption and desorption kinetic studies has revealed important information on the interaction between lead and aluminum (hydr)oxides. This information is valuable for predicting the fate of Pb in the environment.« less
  • No abstract prepared.
  • Sorption processes at the mineral/water interface typically control the mobility and bioaccessibility of many inorganic contaminants such as oxyanions. Selenium is an important micronutrient for human and animal health, but at elevated concentrations selenium toxicity is a concern. The objective of this study was to determine the bonding mechanisms of selenate (SeO{sub 4}{sup 2-}) and selenite (SeO{sub 3}{sup 2-}) on hydrous aluminum oxide (HAO) over a wide range of reaction pH using extended X-ray absorption fine structure (EXAFS) spectroscopy. Additionally, selenate adsorption on corundum ({alpha}-Al{sub 2}O{sub 3}) was studied to determine if adsorption mechanisms change as the aluminum oxide surfacemore » structure changes. The overall findings were that selenite forms a mixture of outer-sphere and inner-sphere bidentate-binuclear (corner-sharing) surface complexes on HAO, selenate forms primarily outer-sphere surface complexes on HAO, and on corundum selenate forms outer-sphere surface complexes at pH 3.5 but inner-sphere monodentate surface complexes at pH 4.5 and above. It is possible that the lack of inner-sphere complex formation at pH 3.5 is caused by changes in the corundum surface at low pH or secondary precipitate formation. The results are consistent with a structure-based reactivity for metal oxides, wherein hydrous metal oxides form outer-sphere complexes with sulfate and selenate, but inner-sphere monodentate surface complexes are formed between sulfate and selenate and {alpha}-Me{sub 2}O{sub 3}.« less