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| 2. |
- Lutzenkirchen, J., et al.
(författare)
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The surface chemistry of sapphire-c: A literature review and a study on various factors influencing its IEP
- 2018
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Ingår i: Advances in Colloid and Interface Science. - : Elsevier BV. - 0001-8686 .- 1873-3727. ; 251, s. 1-25
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Forskningsöversikt (refereegranskat)abstract
- A wide range of isoelectric points (IEPs) has been reported in the literature for sapphire-c (alpha-alumina), also referred to as basal plane, (001) or (0001), single crystals. Interestingly, the available data suggest that the variation of IEPs is comparable to the range of IEPs encountered for particles, although single crystals should be much better defined in terms of surface structure. One explanation for the range of IEPs might be the obvious danger of contaminating the small surface areas of single crystal samples while exposing them to comparatively large solution reservoirs. Literature suggests that factors like origin of the sample, sample treatment or the method of investigation all have an influence on the surfaces and it is difficult to clearly separate the respective, individual effects. In the present study, we investigate cause-effect relationships to better understand the individual effects. The reference IEP of our samples is between 4 and 4.5. High temperature treatment tends to decrease the IEP of sapphire-c as does UV treatment. Increasing the initial miscut (i.e. the divergence from the expected orientation of the crystal) tends to increase the IEP as does plasma cleaning, which can be understood assuming that the surfaces have become less hydrophobic due to the presence of more and/or larger steps with increasing miscut or due to amorphisation of the surface caused by plasma cleaning. Pre-treatment at very high pH caused an increase in the IEP. Surface treatments that led to IEPs different from the stable value of reference samples typically resulted in surfaces that were strongly affected by subsequent exposure to water. The streaming potential data appear to relax to the reference sample behavior after a period of time of water exposure. Combination of the zeta potential measurements with AFM investigations support the idea that atomically smooth surfaces exhibit lower IEPs, while rougher surfaces (roughness on the order of nanometers) result in higher IEPs compared to reference samples. Two supplementary investigations resulted in either surprising or ambiguous results. On very rough surfaces (roughness on the order of micrometers) the IEP lowered compared to the reference sample with nanometer-scale roughness and transient behavior of the rough surfaces was observed. Furthermore, differences in the IEP as obtained from streaming potential and static colloid adhesion measurements may suggest that hydrodynamics play a role in streaming potential experiments. We finally relate surface diffraction data from previous studies to possible interpretations of our electroldnetic data to corroborate the presence of a water film that can explain the low IEP. Calculations show that the surface diffraction data are in line with the presence of a water film, however, they do not allow to unambiguously resolve critical features of this film which might explain the observed surface chemical characteristics like the dangling OH-bond reported in sum frequency generation studies. A broad literature review on properties of related surfaces shows that the presence of such water films could in many cases affect the interfacial properties. Persistence or not of the water film can be crucial. The presence of the water film can in principle affect important processes like ice-nucleation, wetting behavior, electric charging, etc. (C) 2017 Elsevier B.V. All rights reserved.
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- Payne, T. E., et al.
(författare)
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Guidelines for thermodynamic sorption modelling in the context of radioactive waste disposal
- 2013
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Ingår i: Environmental Modelling and Software. - : Elsevier BV. - 1364-8152. ; 42, s. 143-156
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Tidskriftsartikel (refereegranskat)abstract
- Thermodynamic sorption models (TSMs) offer the potential to improve the incorporation of sorption in environmental modelling of contaminant migration. One specific application is safety cases for radioactive waste repositories, in which radionuclide sorption on mineral surfaces is usually described using distribution coefficients (K-d values). TSMs can be utilised to provide a scientific basis for the range of K-d values included in the repository safety case, and for assessing the response of K-d to changes in chemical conditions. The development of a TSM involves a series of decisions on model features such as numbers and types of surface sites, sorption reactions and electrostatic correction factors. There has been a lack of consensus on the best ways to develop such models, and on the methods of determination of associated parameter values. The present paper therefore presents recommendations on a number of aspects of model development, which are applicable both to radioactive waste disposal and broader environmental applications.The TSM should be calibrated using a comprehensive sorption data set for the contaminant of interest, showing the impact of major geochemical parameters including pH, ionic strength, contaminant concentration, the effect of ligands, and major competing ions. Complex natural materials should be thoroughly characterised in terms of mineralogy, surface area, cation exchange capacity, and presence of impurities. During the application of numerical optimisation programs to simulate sorption data, it is often preferable that the TSM should be fitted to the experimentally determined K-d parameter, rather than to the frequently used percentage sorbed. Two different modelling approaches, the component additivity and generalised composite, can be used for modelling sorption data for complex materials such as soils. Both approaches may be coupled to the same critically reviewed aqueous thermodynamic data sets, and may incorporate the same, or similar, surface reactions and surface species. The quality of the final sorption model can be assessed against the following characteristics: an appropriate level of complexity, documented and traceable decisions, internal consistency, limitations on the number of adjustable parameter values, an adequate fit to a comprehensive calibration data set, and capability of simulating independent data sets. Key recommendations for the process of TSM development include: definition of modelling objectives, identification of major decision points, a clear decision-making rationale with reference to experimental or theoretical evidence, utilisation of a suitable consultative and iterative model development process, testing to the maximum practicable extent, and thorough documentation of key decisions. These recommendations are consistent with international benchmarks for environmental modelling.
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| 4. |
- Lützenkirchen, J, et al.
(författare)
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Adsorption of Al13–Keggin clusters to sapphire c-plane single crystals : Kinetic observations by streaming current measurements
- 2010
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Ingår i: Applied Surface Science. - : Elsevier B V. - 0169-4332 .- 1873-5584. ; 256:17, s. 5406-5411
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Tidskriftsartikel (refereegranskat)abstract
- We have carried out streaming current measurements of sapphire c-plane single crystals in contact with the solutions containing the Al13–-Keggin ions at different pH values. We followed the evolution of the zeta-potential as a function of time and pH. The Keggin ions were synthesised and characterised by ESI-MS in two different laboratories, and the results showed that nearly 100% of Al was in the form of Al13 cluster. The streaming current measurements were carried out to investigate whether Al13 clusters would (i) be adsorbed to the surface and (ii) remain stable. Close to the isoelectric point of the sapphire c-plane (around pH 4) it was found that the Al13 ions were adsorbed and stable in the systems for an extended period. After some time the conductivity of the solution strongly increased and the zeta-potential declined, indicating that the clusters were destroyed (certainly in solution, as indicated by the conductivity reading, but potentially also at the surface). ESI-MS measurements at various dilution factors or decreased pH also showed disintegration of the clusters resulting in a multitude of smaller Al species, in agreement with the conductivity measurements during the streaming current measurements. Additions at higher pH showed clear adsorption of the clusters but resulted in stability over the complete observation period as inferred from the conductivity measurements.
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