TY - JOUR A1 - Hünger, K.-J. A1 - Kositz, M. A1 - Danneberg, M. A1 - Radnik, Jörg T1 - Enrichment of aluminium in the near‐surface region of natural quartzite rock after aluminium exposure N2 - Alkali–silica reaction (ASR) is an ongoing problem that causes damage to concrete constructions and reduces their durability. Therefore, minimizing this undesired reaction is of great interest for both safety and economic reasons. Additives containing high aluminium content are very effective in reducing the release of silica and enhancing the durability of concrete; however, the mechanism for this effect is still under discussion. In this study, an enrichment of aluminium in the near‐surface region was observed for natural quartzite rock after storage in Al (OH)3 and metakaolin as aluminium sources, from which we conclude that the formation of aluminosilicate sheets of a few nanometres inhibits the silica release; this hypothesis is supported by high‐resolution spectra of Al 2p, Si 2p and O 1s. KW - Alkali-silica reaction KW - Quartzite rock KW - X-ray photoelectron spectroscopy PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-519394 DO - https://doi.org/10.1002/sia.6918 SN - 0142-2421 SP - 1 EP - 7 PB - Wiley VCH AN - OPUS4-51939 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Weise, Frank A1 - Oesch, T. A1 - Wilsch, Gerd A1 - Sigmund, S. A1 - Hünger, K.-J. A1 - Kositz, M. T1 - Analyse des gefügeabhängigen Löslichkeitsverhaltens potenziell AKR-empfindlicher Gesteinskörnungen T1 - Analysis of the microstructure depending solubility behavior of potential ASR sensitive aggregates N2 - Das gefügeabhängige Löslichkeitsverhalten wurde an folgenden vier Gesteinskörnungen unterschiedlicher Alkaliempfindlichkeitsklassen untersucht: • GK1 (EIII-S): quarzreicher Kies • GK2 (EIII-S): Grauwacke (Splitt) • GK3 (EI-S): Quarz-Feldspat-Porphyr (Splitt) • GK4 (EI-S): sandsteinreicher Kies DiePorenstrukturanalyse erfolgte sowohl an Einzelkörnern mittels vergleichender 3D-CT und BET- Untersuchungen als auch an Korngemengen der einzelnen Kornfraktionen (außer Fraktion 16/22 mm) über die Wasseraufnahme und mit BET. Für die Visualisierung und Quantifizierung der von außen zugänglichen Oberflächenanteile der Einzelkörner wurde ein Softwaretool entwickelt, erprobt und erfolgreich angewandt. Es gelang so u.a. den Nachweis zu erbringen, dass die gebrochenen Einzelkörner der Grauwacke und des Rhyoliths einen deutlich geringeren von außen zugänglichen Oberflächenanteil als die gleichartigen Gesteinskörner aus dem Kies besitzen. Aufgrund der limitierten Ortsauflösung der 3D-CT von 11 bis 16,5 μm wurde mit BET eine um drei Zehnerpotenzen höhere spezifische Oberfläche ermittelt. Zu den Porositätsuntersuchungen an den Korngemengen sei angemerkt, dass zum Teil gegenläufige Trends zwischen offener Porosität und spezifischer Oberfläche festgestellt wurden. Dieses ist beim Bezug des bei den Löseversuchen in 0,1 M KOH mit definierter NaCl-Zugabe aus der Gesteinskörnung gelösten SiO2 und Al2O3 von zentraler Bedeutung. Bei den Löseversuchen an den fraktionsspezifischen Korngemengen selbst zeigte sich, dass die stufenweise Erhöhung des NaCl-Gehalts von 0 auf 10 M.-% im Eluat eine erhöhte SiO2-Löslichkeit und eine verminderte Auslaugung von Al2O3 zur Folge hat. Auffallend war hierbei, dass die Al2O3-Löslichkeit bei GK4 ohne und mit geringer NaCl-Zugabe die mit Abstand höchsten Werte annimmt. Bei den zusätzlich durchgeführten Löseversuchen an den tomografierten Einzelkörnern in 1 M KOH-Lösung mit Zugabe von 1 M.-% NaCl zeigte sich, dass nur vereinzelt bei den untersuchten Gesteinsarten eine Korrelation zwischen dem SiO2- bzw. Al2O3-Gehalt im Eluat und der absoluten BET-Oberfläche nachweisbar ist. Dies ist vermutlich darauf zurückzuführen, dass neben der Oberfläche weitere Parameter (z.B. die mineralogische Zusammensetzung der Einzelkörner) das Löseverhalten maßgebend beeinflussen. Bei den parallel zu den Löseversuchen durchgeführten Betonversuchen nach dem ARS 04/2013 zeigte sich, dass die Alkaliempfindlichkeit der GK4 bei beiden Betonversuchen mit Alkalizufuhr unterschiedlich zu bewerten ist. So ist unabhängig von der vorgegebenen pessimalen Betonrezeptur des Fahrbahndeckenbetons ausschließlich bei der Klimawechsellagerung die GK4 als alkaliempfindlich einzustufen. Allerdings konnte der Befund der stark ausgeprägten AKR bei der GK4 mit der Dünnschliffmikroskopie nicht bestätigt werden. Analoges gilt für die Bewertung der Alkaliempfindlichkeit von GK2 mit den Betonversuchen nach der Alkalirichtlichtlinie des DAfStb. So ist auch hier die GK2 nicht im 60 °C-Betonversuch sondern ausschließlich im 40 °C-Betonversuch als alkaliempfindlich einzustufen. Dienach den verschiedenartigen Betonversuchen durchgeführten LIBS-Analysen am Vertikalschnitt der Prüfkörper zeigen, dass im Kernbereich nach dem 60 °C-Betonversuch mit 10 %iger NaCl-Lösung und nach der Klimawechsellagerung mit NaCl-Beaufschlagung annähernd gleich hohe Natrium- und Chloridgehalte vorgefunden werden. Wider Erwarten treten an den beaufschlagten Prüfflächen Abreicherungen von Natrium und Anreicherungen von Chlorid auf. Im 40°C- und 60 °C-Betonversuch wurde das Natrium bis in eine maximale Tiefe von ca. 30 mm bzw. 20 mm ausgelaugt. Die aufbauenden korrelativen Betrachtungen zwischen den Ergebnissen des 60°C Betonversuchs mit Alkalizufuhr und der Löseversuche an den fraktionsspezifischen Korngemengen in 1 M KOH-Lösung mit definierter NaCl-Zugabe sind durchaus vielversprechend. So zeigt sich beispielsweise beim Waschbeton, dass der fraktionsspezifisch gewichtete SiO2-Überschuss im Eluat nach 56 Tagen mit Zugabe von 0,5 M.-% NaCl ohne Bezug auf die BET-Oberfläche zur gleichen Einstufung der vier betrachteten Gesteinskörnungen wie bei den Dehnungen im 60 °C-Betonversuch mit 3 %-iger NaCl-Lösung führt. Außerdem korrelieren die im 60 °C-Betonversuch mit 10 %-iger NaCl-Lösung ermittelten Dehnungen mit dem gewichteten SiO2-Überschuss im Eluat bei Zugabe von 2 M.-% NaCl ohne Bezug auf die BET-Oberfläche. Ausschließlich bei den Betonversuchen nach der Alkali-Richtlinie erwies sich der Bezug des im Eluat ermittelten SiO2-Überschusses auf die BET-Oberfläche als zielführend. Aufgrund des Potenzials der Löseversuche mit NaCl-Zugabe für die Bewertung der Alkaliempfindlichkeit der Gesteinskörnung im Fahrbahndeckenbeton wird empfohlen, die vergleichenden Untersuchungen zwischen den Löseversuchen an Korngemischen der einzelnen Fraktionen und den Betonversuchen nach dem ARS 04/2013 mit einer möglichst hohen Anzahl an Gesteinskörnungen und einem präzisierten Untersuchungsumfang fortzuführen. N2 - The following four aggregates (GK) of varying grades of alkali sensitivity were examined for their microstructure-dependent solubility behavior: • GK1 (EIII-S) gravel with high quarz content • GK2 (EIII-S) greywacke (crushed stone) • GK3 (EI-S) quarz-feldspar-porphyry (crushed stone) • GK4 (EI-S) gravel with high sandstone content Pore structure analysis was carried out both on single grains using comparative 3D-CT and BET tests, and on grain samples of individual grain fractions (excluding the 16/22 mm fraction) using water absorption and BET. A software tool for visualizing and quantifying the externally accessible surfaces of single grains was developed, tested and successfully applied. This enabled us, among other things, to prove that single broken grains of greywacke and rhyolite have a much smaller externally accessible surface than grains of gravel of the same aggregate fraction. Due to the 3D-CT’s limited spatial resolution of 11 to 16.5 μm, BET was used to determine a two to three powers of ten higher specific surface. In relation to the porosity tests of the grain samples, it should be noted that in some cases, counterdirectional trends between open porosity and specific surface were determined. This is of central importance in relation to the SiO2 and Al2O3 dissolved from the aggregate in the solubility tests in 1 M KOH with defined addition of NaCl. The solubility tests on the grain samples of specific fractions showed that the gradual increase of the NaCl content in the eluate from 0 to 10 M.-% resulted in increased SiO2 solubility and reduced leaching of Al2O3. It was striking in this context that the solubility of Al2O3 in GK4 with no or little addition of NaCl gives by far the highest values. The additional solubility tests carried out on single grains, that were previously subjected to CT testing, in 1 M KOH solution with 1 M.-% added NaCl showed that in the types of aggregate examined, a correlation between the SiO2 and Al2O3 in eluate and the absolute BET surface is only occasionally demonstrable. This is probably due to the fact that solubility behavior is decisively influenced by other parameters in addition to the surface (e.g. by the mineralogical composition of individual grains). The concrete tests according to ARS 04/2013 carried out parallel to the solubility tests showed that GK4’s alkali sensitivity in both concrete tests with added alkali must be evaluated differently. For example, independent of the prescribed pessimal road surface concrete formula, GK4 can only be classified as alkali sensitive under cyclic storage. However petrographic microscopy could not confirm the findings of very marked ASR in GK4. The same applies to the evaluation of alkali sensitivity in GK2 with the concrete tests according to the German Committee for Structural Concrete (DAfStb)’s Alkali Guidelines. In this case too, GK2 should not be classified as alkali sensitive in 60 °C concrete testing, but only in 40 °C concrete testing. The LIBS analyses carried out on the vertical cross-section of the test specimens after the various concrete tests showed that almost equally high sodium and chloride levels were found in the core area after the 60 °C concrete prism test with 10 % NaCl solution and after cyclic storage with NaCl application. Contrary to expectations, the surfaces of samples after NaCl application showed a decrease in sodium and an increase in chloride. In the 40°C and 60°C concrete prism tests, sodium was depleted up to a maximum depth of approx. 30 mm and 20 mm respectively. Subsequent correlative observations between the findings of the 60°C concrete prism test with alkali application, and the solubility tests on the samples of specific grain fractions in 1 M KOH solution with defined NaCl addition, are very promising. In the case of exposed aggregate concrete, for example, the fraction-specific weighted excess SiO2 to in the eluate after 56 days with added 0.5 M.-% NaCl unrelated to the BET surface results in the same classification of the four aggregates examined as the expansions in the 60 °C concrete prism test with 3% NaCl solution. In addition, the expansions found in the 60 °C concrete prism test with 10% NaCl solution correlated with the weighted excess SiO2 in eluate with added 2 M.-% NaCl without relation to the BET surface. Only in the case of the concrete test in accordance with the Alkali Guidelines did the relationship of the excess SiO2 in the eluate to the BET surface prove to be productive. Due to the potential of the solubility test with added NaCl for the evaluation of alkali sensitivity of aggregates in road surface concrete, we recommend continuing with comparative tests between solubility tests of grain samples of the various fractions and the concrete tests in accordance with ARS O4/13 with the greatest possible number of aggregates and a precisely defined investigation scope. KW - LIBS KW - Betonfahrbahndecke KW - Alkali-Kieselsäure-Reaktion KW - Gesteinskörnung KW - Alkaliempfindlichkeit KW - 3D-CT KW - Tausalzeintrag PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:hbz:opus-bast-25832 UR - https://bast.opus.hbz-nrw.de/frontdoor/index/index/docId/2583 SN - 978-3-95606-648-1 SN - 0943-9323 VL - S 165 SP - 1 EP - 111 PB - Fachverlag NW in der Carl Ed. Schünemann KG CY - Bremen AN - OPUS4-54755 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kositz, M. A1 - Hünger, K.-J. A1 - Weise, Frank T1 - Regression analysis of ASR expansions and silica dissolution in the presence of NaCl N2 - The durability of concrete structures due to alkali-silica-reaction (ASR) is usually been assessed by ASR concrete prism tests (CPT). Therefore, the expansion of concrete specimens indicates an alkalisensitivity. In Germany these tests are performed at 40°C or accelerated 60°C. Nevertheless, ASR prism tests are expensive, power and time-consuming. For these reasons, an alternative chemical test (“mod. BTU-test”) was developed in the past. The “mod. BTU-test” was correlated with German standard CPT. In this test, the solubility of silica and alumina in the liquid phase is measured by ICP-OES. For special requirements in concrete road construction, stricter test procedures are necessary. The specimens are repeatedly subjected to cyclic alternating storage in NaCl. On the one hand, the presence of NaCl increases the ASR expansion, on the other hand NaCl also changes the dissolution behaviour of silica and alumina. For now is not possible to correlate the solubilities of “mod. BTU-test” and ASR expansions influenced by NaCl. Therefore, four aggregates with different ASR sensitivities were chosen and ASR concrete prism tests (in addition with NaCl) have been performed. According to the “mod. BTU-test” the solubilities of silica and alumina in presence of different NaCl concentrations were measured. This paper is about the regression analysis of silica and alumina dissolution and ASR expansion tests in presence of NaCl. The regression analysis shows the influence of a quasi-continuous and an interrupted cyclic alternating storage. Additionally the effects of temperature and NaCl concentration are investigated. In the end, a suitable NaCl concentration of the “mod. BTU-test” for dissolution experiments is recommended. The “mod. BTU-Test” with NaCl might be a serious and reliable test method for ASR classification for concrete road construction. T2 - 16th International Conference on Alkali-Aggregate Reaction in Concrete CY - Lisboa, Portugal DA - 31.05.2022 KW - Alkali silica reaction KW - Alkaline solution KW - Alumina & silica dissolution KW - NaCl KW - Regression analysis PY - 2021 SN - 978-972-49-2315-4 VL - 1 SP - 711 EP - 723 AN - OPUS4-54552 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Greiser, Sebastian A1 - Hunger, M. A1 - Jäger, Christian T1 - 29Si{27Al} TRAPDOR MAS NMR to distinguish Qn(mAl) sites in aluminosilicates. Test case: Faujasite-type zeolites N2 - 29Si{27Al} TRAPDOR MAS NMR was applied to two faujasite-type zeolites with Si/Al ratios of 1.3 (Na-X) and 2.7 (Na-Y). The aim of this test study is to show that different Q4(mAl) sites (m=4,3,2,1) can be distinguished by differently strong TRAPDOR effects (ΔS/S0). Indeed, it was found that the TRAPDOR effect depends on the number m of AlO4 units connected to the Q4 silicon tetrahedrons. For Na-X, the measured ΔS/S0 values are 1:0.81:0.56 for Q4(4Al), Q4(3Al) and Q4(2Al), respectively (normalized to Q4(4Al)). The corresponding ΔS/S0 values are the same for Na-Y within the error bars, although the silicon sites are different: Q4(3Al), Q4(2Al) and Q4(1Al) and now normalized to Q4(3Al) as no Q4(4Al) is present. Nevertheless, the proposed method opens up the possibility to distinguish overlapping 29Si NMR signals of the Qn(mAl) sites in amorphous materials as the main goal of these investigations. KW - Solid-state NMR KW - 29Si{27Al} TRAPDOR MAS NMR KW - Q4(mAl) sites KW - Faujasite-type zeolites KW - Aluminosilicates PY - 2016 DO - https://doi.org/10.1016/j.ssnmr.2016.10.004 SN - 0926-2040 SN - 1527-3326 VL - 80 SP - 6 EP - 10 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-38718 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Priebe, Nsesheye Susan A1 - Vogler, Nico A1 - Sturm, Patrick A1 - Neubert, M. A1 - Schröder, H.-J. A1 - Kühne, Hans-Carsten A1 - Hünger, K.-J. A1 - Gluth, Gregor T1 - Calcined brick clays and mixed clays as supplementary cementitious materials: Effects on the performance of blended cement mortars N2 - While calcined clays in general have been credited with a great potential to mitigate CO2 emissions related to cement production and consumption, calcined brick clays are currently understudied in this regard. In the present work, two brick clays, a low-grade kaolinitic clay, and a mixed clay composed of 50% brick clay and 50% low-grade kaolinitic clay were studied regarding transformations on calcination, and strength and durability performance as well as pore structure of mortars made with the blended cements. All calcined clays exhibited pozzolanic reactivity, with the performance of the brick clays inferior to the low-grade kaolinitic clay. However, the mixed clay performed very similar to the low-grade kaolinitic clay, which points to a viable option for optimal use of brick clays in cementitious systems. The carbonation resistance of the blended cement mortars was generally worse than that of the plain Portland cement mortar, as expected, but the former exhibited a significantly improved chloride penetration resistance. The latter improvement was due to pore structure refinement in the blended cement mortars, compared to the Portland cement mortar. KW - Brick clay KW - Illitic clay KW - Calcined clay KW - Blended cement KW - Supplementary cementitous materials PY - 2021 DO - https://doi.org/10.1016/j.conbuildmat.2020.120990 N1 - Geburtsname von Priebe, Nsesheye Susan: Msinjili, N. S. - Birth name of Priebe, Nsesheye Susan: Msinjili, N. S. VL - 266 SP - 120990 PB - Elsevier Ltd. AN - OPUS4-51362 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Greiser, Sebastian A1 - Sturm, Patrick A1 - Gluth, Gregor A1 - Hunger, M. A1 - Jäger, Christian T1 - Differentiation of the solid-state NMR signals of gel, zeolite phases and water species in geopolymer-zeolite composites N2 - Geopolymer-zeolite composites were synthesized using a silica-rich industrial byproduct from chlorosilane production and sodium aluminate. Pastes were cured at 80 °C and 80% RH, and subsequently dried in two different climates: at 23 °C and 50% RH, and under vacuum. 1H MAS, 23Na MAS and 29Si MAS NMR and XRD measurements were performed after the drying procedures as well as after subsequent aging. Zeolite Na-A was found beside traces of faujasite-type zeolite and zeolite EMT as major crystalline phases in the cured composites; the fraction of geopolymeric gel in the reaction products was determined to be ~18% on a molar basis. Various water species could be distinguished using 1H MAS and 1H-29Si CP MAS NMR, applying rotorsynchronized echo experiments. The largest fraction of the pore water resides in the α-cages of the zeolite Na-A and in the geopolymeric gel; in addition, water exists in the β-cages of the zeolites and adsorbed at sodium ions. The water species in α-cages and in the pores of the geopolymeric gel exhibit slightly different chemical shifts of 4.7 ppm and 4.9 ppm, respectively, in the 1H MAS NMR spectra. Changes of the water content in the geopolymer pores of differently dried samples were observed and led to slightly varied chemical shifts in the 29Si MAS NMR spectra too. Measurements after more than 500 days revealed no significant aging effects of the composites, which confirm their chemical stability. KW - Geopolymers KW - Aluminosilicate inorganic polymers KW - Zeolite Na-A KW - Spectroscopy KW - Drying PY - 2017 DO - https://doi.org/10.1016/j.ceramint.2016.11.004 SN - 0272-8842 VL - 43 IS - 2 SP - 2202 EP - 2208 PB - Elsevier AN - OPUS4-38694 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -