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Chernyshev, A. N., Jonsson, M. & Forsberg, K. (2018). Characterization and degradation of a polyaryl ether based superplasticizer for use in concrete barriers in deep geological repositories. Applied Geochemistry, 95, 172-181
Open this publication in new window or tab >>Characterization and degradation of a polyaryl ether based superplasticizer for use in concrete barriers in deep geological repositories
2018 (English)In: Applied Geochemistry, ISSN 0883-2927, E-ISSN 1872-9134, Vol. 95, p. 172-181Article in journal (Refereed) Published
Abstract [en]

Superplasticizers are important additives used in concrete barriers in geological waste repositories. Superplasticizers have been a major concern in the long-term assessments of safe geological disposal for radioactive waste since superplasticizers and their degradation products can act as complexing ligands and thereby increase the mobility of radionuclides. In this work a new type of superplasticizer, based on a polyaryl ether polymer, has been characterized. It was found that the superplasticizer combines the structural features of polycarboxylate ether based superplasticizers and sulfonated naphthalene-formaldehyde based superplasticizers and that it contains organophosphatecharged groups. A novel method for evaluating the rate of degradation of the superplasticizer under alkaline conditions was elaborated and the degradation products and rate constant of the process was determined. The results demonstrate that degradation occurs rapidly compared to the typical lifetime of a repository.

Place, publisher, year, edition, pages
Elsevier, 2018
Keywords
Waste disposal; Alkaline degradation; Polyaryl ether based superplasticizer
National Category
Chemical Engineering Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-228236 (URN)10.1016/j.apgeochem.2018.05.014 (DOI)000437294900015 ()2-s2.0-85048180279 (Scopus ID)
Funder
Swedish Nuclear Fuel and Waste Management Company, SKB
Note

QC 20180611

Available from: 2018-05-20 Created: 2018-05-20 Last updated: 2018-11-28Bibliographically approved
Norrfors, K. K., Björkbacka, Å., Kessler, A., Wold, S. & Jonsson, M. (2018). γ-radiation induced corrosion of copper in bentonite-water systems under anaerobic conditions. Radiation Physics and Chemistry, 144, 8-12
Open this publication in new window or tab >>γ-radiation induced corrosion of copper in bentonite-water systems under anaerobic conditions
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2018 (English)In: Radiation Physics and Chemistry, ISSN 0969-806X, E-ISSN 1879-0895, Vol. 144, p. 8-12Article in journal (Refereed) Published
Abstract [en]

In this work we have experimentally studied the impact of bentonite clay on the process of radiation-induced copper corrosion in anoxic water. The motivation for this is to further develop our understanding of radiation-driven processes occurring in deep geological repositories for spent nuclear fuel where copper canisters containing the spent nuclear fuel will be embedded in compacted bentonite. Experiments on radiation-induced corrosion in the presence and absence of bentonite were performed along with experiments elucidating the impact irradiation on the Cu2+ adsorption capacity of bentonite. The experiments presented in this work show that the presence of bentonite clay has no or very little effect on the magnitude of radiation-induced corrosion of copper in anoxic aqueous systems. The absence of a protective effect similar to that observed for radiation-induced dissolution of UO2 is attributed to differences in the corrosion mechanism. This provides further support for the previously proposed mechanism where the hydroxyl radical is the key radiolytic oxidant responsible for the corrosion of copper. The radiation effect on the bentonite sorption capacity of Cu2+ (reduced capacity) is in line with what has previously been reported for other cations. The reduced cation sorption capacity is partly attributed to a loss of Al-OH sites upon irradiation.

Place, publisher, year, edition, pages
Elsevier Ltd, 2018
Keywords
Aluminum compounds, Anoxic sediments, Copper, Copper corrosion, Corrosion, Irradiation, Positive ions, Radiation, Adsorption capacities, Anaerobic conditions, Compacted bentonite, Corrosion mechanisms, Deep geological repository, Protective effects, Sorption capacities, Spent nuclear fuels, Bentonite, hydroxyl radical, nuclear fuel, adsorption kinetics, anaerobic capacity, Article, embedding, environmental impact assessment, gamma radiation, water supply
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-223137 (URN)10.1016/j.radphyschem.2017.11.004 (DOI)000423646400002 ()2-s2.0-85034661878 (Scopus ID)
Funder
Swedish Nuclear Fuel and Waste Management Company, SKB
Note

Export Date: 13 February 2018; Article; CODEN: RPCHD; Correspondence Address: Jonsson, M.; School of Chemical Science and Engineering, Applied Physical Chemistry, KTH Royal Institute of TechnologySweden; email: matsj@kth.se; Funding details: SKB, Svensk Kärnbränslehantering. QC 20180326

Available from: 2018-03-26 Created: 2018-03-26 Last updated: 2018-03-26Bibliographically approved
Yang, M., Soroka, I. & Jonsson, M. (2017). Exploring the limitations of the Hantzsch method used for quantification of hydroxyl radicals in systems of relevance for interfacial radiation chemistry. Radiation Physics and Chemistry, 130, 1-4
Open this publication in new window or tab >>Exploring the limitations of the Hantzsch method used for quantification of hydroxyl radicals in systems of relevance for interfacial radiation chemistry
2017 (English)In: Radiation Physics and Chemistry, ISSN 0969-806X, E-ISSN 1879-0895, Vol. 130, p. 1-4Article in journal (Refereed) Published
Abstract [en]

In the presence of Tris or methanol, hydroxyl radicals in systems of relevance for interfacial radiation chemistry can be quantified indirectly via the Hantzsch method by determining the amount of the scavenging product formaldehyde formed. In this work, the influence of the presence of H2O2 on the Hantzsch method using acetoacetanilide (AAA) as derivatization reagent is studied. The experiments show that the measured CH2O concentration deviates from the actual concentration in the presence of H2O2 and the deviation increases with increasing [H2O2]0/[CH2O]0. The deviation is negative, i.e., the measured formaldehyde concentration is lower than the actual concentration. This leads to an underestimation of the hydroxyl radical production in systems containing significant amount of H2O2. The main reason for the deviation is found to be three coupled equilibria involving H2O2, CH2O and the derivative produced in the Hantzsch method.

Place, publisher, year, edition, pages
Elsevier, 2017
Keywords
Acetoacetanilide, Formaldehyde, Hantzsch method, Hydrogen peroxide, Hydroxyl radical, Derivatization reagent, Formaldehyde concentrations, Hantzsch, Hydroxyl radicals, Radiation chemistry, acetanilide derivative, unclassified drug, Article, chemical analysis, chemical reaction kinetics, concentration (parameters), controlled study, interfacial radiation chemistry, quantitative analysis, radiochemistry
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-195129 (URN)10.1016/j.radphyschem.2016.07.021 (DOI)000388777200001 ()2-s2.0-84979622715 (Scopus ID)
Note

QC 20161121

Available from: 2016-11-21 Created: 2016-11-02 Last updated: 2017-11-29Bibliographically approved
Nilsson, K., Roth, O. & Jonsson, M. (2017). Oxidative dissolution of ADOPT compared to standard UO2 fuel. Journal of Nuclear Materials, 488, 123-128
Open this publication in new window or tab >>Oxidative dissolution of ADOPT compared to standard UO2 fuel
2017 (English)In: Journal of Nuclear Materials, ISSN 0022-3115, E-ISSN 1873-4820, Vol. 488, p. 123-128Article in journal (Refereed) Published
Abstract [en]

In this work we have studied oxidative dissolution of pure UO2 and ADOPT (UO2 doped with Al and Cr) pellets using H2O2 and gammaradiolysis to induce the process. There is a small but significant difference in the oxidative dissolution rate of UO2 and ADOPT pellets, respectively. However, the difference in oxidative dissolution yield is insignificant. Leaching experiments were also performed on in-reactor irradiated ADOPT and UO2 pellets under oxidizing conditions. The results indicate that the U(VI) release is slightly slower from the ADOPT pellet compared to the UO2. This could be attributed to differences in exposed surface area. However, fission products with low UO2 solubility display a higher relative release from ADOPT fuel compared to standard UO2-fuel. This is attributed to a lower matrix solubility imposed by the dopants in ADOPT fuel. The release of Cs is higher from UO2 which is attributed to the larger grain size of ADOPT. © 2017 Elsevier B.V.

Place, publisher, year, edition, pages
Elsevier B.V., 2017
Keywords
Doping (additives), Fission products, Fuels, Pelletizing, Solubility, Exposed surfaces, Grain size, Leaching experiments, Matrix solubility, Oxidative dissolution, Oxidizing conditions, Dissolution
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-207344 (URN)10.1016/j.jnucmat.2017.02.044 (DOI)000400218100012 ()2-s2.0-85015707126 (Scopus ID)
Note

QC 20170522

Available from: 2017-05-22 Created: 2017-05-22 Last updated: 2017-05-23Bibliographically approved
Lousada, C. M., Soroka, I. L., Yagodzinskyy, Y., Tarakina, N. V., Todoshchenko, O., Hänninen, H., . . . Jonsson, M. (2016). Gamma radiation induces hydrogen absorption by copper in water. Scientific Reports, 6, Article ID 24234.
Open this publication in new window or tab >>Gamma radiation induces hydrogen absorption by copper in water
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2016 (English)In: Scientific Reports, ISSN 2045-2322, E-ISSN 2045-2322, Vol. 6, article id 24234Article in journal (Refereed) Published
Abstract [en]

One of the most intricate issues of nuclear power is the long-term safety of repositories for radioactive waste. These repositories can have an impact on future generations for a period of time orders of magnitude longer than any known civilization. Several countries have considered copper as an outer corrosion barrier for canisters containing spent nuclear fuel. Among the many processes that must be considered in the safety assessments, radiation induced processes constitute a key-component. Here we show that copper metal immersed in water uptakes considerable amounts of hydrogen when exposed to γ-radiation. Additionally we show that the amount of hydrogen absorbed by copper depends on the total dose of radiation. At a dose of 69 kGy the uptake of hydrogen by metallic copper is 7 orders of magnitude higher than when the absorption is driven by H2(g) at a pressure of 1 atm in a non-irradiated dry system. Moreover, irradiation of copper in water causes corrosion of the metal and the formation of a variety of surface cavities, nanoparticle deposits, and islands of needle-shaped crystals. Hence, radiation enhanced uptake of hydrogen by spent nuclear fuel encapsulating materials should be taken into account in the safety assessments of nuclear waste repositories.

Place, publisher, year, edition, pages
Nature Publishing Group, 2016
National Category
Manufacturing, Surface and Joining Technology Physical Sciences
Identifiers
urn:nbn:se:kth:diva-187004 (URN)10.1038/srep24234 (DOI)000374226400001 ()2-s2.0-84964306889 (Scopus ID)
Note

QC 20160523

Available from: 2016-05-23 Created: 2016-05-16 Last updated: 2017-11-30Bibliographically approved
Dispenza, C., Sabatino, M. A., Grimaldi, N., Mangione, M. R., Walo, M., Murugan, E. & Jonsson, M. (2016). On the origin of functionalization in one-pot radiation synthesis of nanogels from aqueous polymer solutions. RSC Advances, 6(4), 2582-2591
Open this publication in new window or tab >>On the origin of functionalization in one-pot radiation synthesis of nanogels from aqueous polymer solutions
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2016 (English)In: RSC Advances, ISSN 2046-2069, E-ISSN 2046-2069, Vol. 6, no 4, p. 2582-2591Article in journal (Refereed) Published
Abstract [en]

Radiation-engineered poly(N-vinyl pyrrolidone) nanogels are very interesting biocompatible nanocarriers for i.v. administration of therapeutics and contrast agents for bioimaging. The manufacturing process is fast and effective, it grants excellent control of particle size and simultaneous sterilization of the formed nanogels. Interestingly, primary amino groups and carboxyl groups, useful for (bio) conjugation, are also formed in a dose-dependent fashion. In this paper, by means of both numerical simulations and experiments, the origin of nanogel size control and functionalization is investigated. This understanding offers a new dimension for the design and production of radiation-sculptured multifunctional nanocarriers from aqueous solutions of polymers.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2016
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-182875 (URN)10.1039/c5ra23926e (DOI)000368193500008 ()2-s2.0-84954058310 (Scopus ID)
Note

QC 20160224

Available from: 2016-02-24 Created: 2016-02-23 Last updated: 2017-11-30Bibliographically approved
Fidalgo, A. B., Dahlgren, B., Brinck, T. & Jonsson, M. (2016). Surface Reactions of H2O2, H-2, and O-2 in Aqueous Systems Containing ZrO2. The Journal of Physical Chemistry C, 120(3), 1609-1614
Open this publication in new window or tab >>Surface Reactions of H2O2, H-2, and O-2 in Aqueous Systems Containing ZrO2
2016 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 120, no 3, p. 1609-1614Article in journal (Refereed) Published
Abstract [en]

In radiolysis of water, three molecular products are formed (H2O2, O-2, and H-2). It has previously been shown that aqueous hydrogen peroxide is catalytically decomposed on many oxide surfaces and that the decomposition proceeds via the formation of surface-bound hydroxyl radicals. In this work, we have investigated the behavior of aqueous H-2 and O-2 in contact with ZrO2. Experiments were carried out in an autoclave with high H2 pressure and low O-2 pressure (40 and 0.2 bar, respectively). In the experiments the concentration of H-abstracting radicals was monitored as a function of time using tris(hydroxymethyl)aminomethane (Tris) as scavenger and the subsequent formation of formaldehyde to probe radical formation. The plausible formation of H2O2 was also monitored in the experiments. In addition, density functional theory (employing the hybrid PBE0 functional) was used to search for reaction pathways. The results from the,experiments show that hydrogen-abstracting radicals: are formed in the aqueous H2O2-system in contact with solid ZrO2. Formation of H2O2 is also detected, and the time dependent production of hydrogen-abstracting radicals follows the time-dependent H2O2 concentration, strongly:indicating that the radicals are produced upon catalytic decomposition of H2O2. The DFT study implies that H2O2 formation proceeds via a pathway where HO2 is a key intermediate. It is interesting to note that all the stable molecular products from aqueous radiolysis are precursors of quite intriguing radical reactions at water/oxide interfaces.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2016
National Category
Engineering and Technology Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-182780 (URN)10.1021/acs.jpcc.5b10491 (DOI)000369116100026 ()2-s2.0-84956691050 (Scopus ID)
Note

QC 20160223

Available from: 2016-02-23 Created: 2016-02-23 Last updated: 2017-04-21Bibliographically approved
Lousada, C. M., Brinck, T. & Jonsson, M. (2015). Application of reactivity descriptors to the catalytic decomposition of hydrogen peroxide at oxide surfaces. Computational and Theoretical Chemistry, 1070, 108-116
Open this publication in new window or tab >>Application of reactivity descriptors to the catalytic decomposition of hydrogen peroxide at oxide surfaces
2015 (English)In: Computational and Theoretical Chemistry, ISSN 2210-271X, E-ISSN 2210-2728, Vol. 1070, p. 108-116Article in journal (Refereed) Published
Abstract [en]

We have employed density functional theory (DFT) calculations using the PBE0 functional to study the reaction of decomposition of H2O2 on clusters of: ZrO2, TiO2, Y2O3, Fe2O3, CeO2, CuO, Al2O3, NiO2, PdO2 and Gd2O3. The formation of the products of decomposition of H2O2 and their binding onto these oxides are discussed. The obtained energy barriers for H2O2 decomposition deviate from experimental data in absolute average by 4 kJ mol(-1). The only exceptions are CeO2 and Fe2O3 for which the deviations are very large. The adsorption of HO radicals onto the clusters was also studied. Reactivity descriptors obtained with DFT calculations are correlated with experimental data from literature. We found a direct correlation between the adsorption energy of HO radicals and the change in Mulliken charge of the cation present in the oxide, upon adsorption of these radicals. Other DFT and experimentally obtained reactivity descriptors based on properties of the cations present in the oxides, such as the ionization potential and electronegativity are plotted against experimental and DFT computed properties, respectively. Following the Bronsted-Evans Polanyi principle, there is a correlation between the adsorption energy of the product HO radical and the energy barrier for decomposition of H2O2. The good correlations between experimental data and the data obtained with DFF using minimalistic cluster models of the oxides surfaces indicates that on the real systems the processes that determine the reactivity of H2O2 are very dependent on localized properties of the surfaces.

Place, publisher, year, edition, pages
Elsevier, 2015
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-119809 (URN)10.1016/j.comptc.2015.08.001 (DOI)000361576000016 ()2-s2.0-84941272843 (Scopus ID)
Note

Updated from "In press" to "Published". QC 20151207. QC 20160304

Available from: 2013-03-22 Created: 2013-03-22 Last updated: 2017-12-06Bibliographically approved
Yang, M., Soroka, I. & Jonsson, M. (2015). Hydroxyl radical production in aerobic aqueous solution containing metallic tungsten. Catalysis communications, 71, 93-96
Open this publication in new window or tab >>Hydroxyl radical production in aerobic aqueous solution containing metallic tungsten
2015 (English)In: Catalysis communications, ISSN 1566-7367, E-ISSN 1873-3905, Vol. 71, p. 93-96Article in journal (Refereed) Published
Abstract [en]

Abstract In this work, we investigate the production of hydroxyl radicals from the W(s)/air aqueous system by quantifying the amount of scavenging product formaldehyde via the modified Hantzsch method. Tris(hydroxymethyl) aminomethane (Tris) and methanol are used as probe for HO. Meanwhile, the amount of dissolved tungsten is determined by ICP-OES. A turnover point ([W] ≈ 200 μM) is observed in the Tris case after which the production rate of CH2O overwhelms the constant rate in the methanol case. Based on the results, a mechanism is proposed for the studied system including both surface and solution reactions.

Keywords
Hydroxyl radical, Tungsten, H2O2, Oxidative dissolution, Haber–Weiss peroxide chain breakdown
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-173119 (URN)10.1016/j.catcom.2015.08.026 (DOI)000362607000020 ()2-s2.0-84940653659 (Scopus ID)
Note

QC 20150922

Available from: 2015-09-07 Created: 2015-09-07 Last updated: 2017-12-04Bibliographically approved
Yang, M., Zhang, X., Grosjean, A., Soroka, I. & Jonsson, M. (2015). Kinetics and Mechanism of the Reaction between H2O2 and Tungsten Powder in Water. The Journal of Physical Chemistry C, 119(39), 22560-22569
Open this publication in new window or tab >>Kinetics and Mechanism of the Reaction between H2O2 and Tungsten Powder in Water
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2015 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 119, no 39, p. 22560-22569Article in journal (Refereed) Published
Abstract [en]

In this work, the reaction between H2O2 and tungsten powder in the presence of Tris(hydroxymethyl) aminomethane was studied experimentally. The production of hydroxyl radicals can be quantified indirectly by quantifying the scavenging product formaldehyde (CH2O). XRD, XPS, and SEM analysis shows that no significant structural or compositional changes occur after reaction. We compared H2O2 consumption and CH2O formation in both heterogeneous W(s)/H2O2/Tris system and homogeneous W(aq)/H2O2/Tris system. Increasing the amount of W powder leads to the increase in dissolution rate of W species, insignificant increase of H2O2 consumption rate and the decrease of final CH2O production. By contrast, the consumption rate of H2O2 increases as increasing the concentration of dissolved W species. Based on the experimental results, a mechanism of H2O2 reacting with W powder in the presence of Tris is proposed. The mechanism well explained the relationship between surface reactions and homogeneous Haber–Weiss peroxide chain breakdown.

National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-173748 (URN)10.1021/acs.jpcc.5b07012 (DOI)000362385700034 ()2-s2.0-84942761051 (Scopus ID)
Note

QC 20150922

Available from: 2015-09-17 Created: 2015-09-17 Last updated: 2017-05-30Bibliographically approved
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ORCID iD: ORCID iD iconorcid.org/0000-0003-0663-0751

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