6 Materialchemie
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- Cement (6)
- Alkali-activated materials (4)
- Early hydration (4)
- Acid resistance (3)
- Polycarboxylate ether (3)
- Polycarboxylate ether (PCE) (3)
- Polymers of intrinsic microporosity (3)
- Abwasserinfrastruktur (2)
- Alkaliaktivierte Bindemittel (2)
- Anlagensicherheit (2)
- BDS (2)
- Biogene Schwefelsäurekorrosion (2)
- C3A (2)
- C3A hydration (2)
- Cement hydration (2)
- Delayed addition (2)
- Dielectric spectroscopy (2)
- Dye (2)
- Fließmittel (2)
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- Legierungen (2)
- Neutron Scattering (2)
- Optical Spectroscopy (2)
- Polycarboxylatether (2)
- Polymers with intrinsic microporosity (2)
- Reparatursysteme (2)
- Rheologie (2)
- Zementleim (2)
- Ageing (1)
- Alite (1)
- Aqueous phase of cement paste (1)
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- Berliner Tuffsteinfassaden (1)
- Betondickglasfenster des Glockenturms am Eiermannbau (1)
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- Corrosion (1)
- Distribution of nanoparticles (1)
- EC4SafeNano (1)
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- Ettringen tuff (1)
- Fast scanning calorimeter (1)
- Fast scanning calorimetry (1)
- Filled rubbers (1)
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- Fluorescence Spectroscopy (1)
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- Gas separation membranes (1)
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- Gold mit Synchrotronstrahlung (1)
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- Kaiser-Wilhelm-Gedächtniskirche (1)
- Kandelaber des Ensembles am Charlottenburger Tor (1)
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- Polycarboxylate ether (PCE), (1)
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- Quasielastic neutron scattering (1)
- Radiografische Untersuchung (1)
- Rainfall simulator (1)
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- X-ray photoelectron spectroscopy (1)
- XPS (1)
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- dielectric spectroscopy (1)
- gas separation membranes (1)
- molecular mobility (1)
- polymers (1)
- polymers of intrinsic microporosity (1)
- polynorbornenes (1)
Organisationseinheit der BAM
- 7 Bauwerkssicherheit (44) (entfernen)
Eingeladener Vortrag
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Durch Auslagerungs- und elektrochemische Tests im Labor kann das Korrosionsverhalten verschiedener metallener Werkstoffe beurteilt werden. Aus den Versuchsergebnissen, die in verschiedenen synthetischen Geothermalwässern im Labor erzielt wurden, lassen sich die folgenden Schlussfolgerungen ziehen:
• Die Anfälligkeit für Spaltkorrosion wurde als wichtigster Aspekt für die Werkstoffqualifizierung ermittelt.
• Der niedriglegierte Stahl 25CrMo4 zeigte bei niedrigem Salzgehalt in MB-Geothermalwasser eine gleichmäßige Korrosion unterhalb der akzeptierten Schwelle von 0,3 mm/Jahr. Daher kann er als geeignet für geothermische Bedingungen mit niedrigem Salzgehalt angesehen werden, wie sie für MB getestet wurden. Es besteht keine Notwendigkeit, auf höherlegierte (teurere) Werkstoffe auszuweichen. Ein niedrigerer pH-Wert (wie bei LHD) führt zu Korrosionsraten oberhalb der akzeptablen Grenzwerte, so dass die niedriglegierten Werkstoffe nicht für Flüssigkeiten mit niedrigem pH-Wert geeignet sind.
• Stark salzhaltige Geothermalwässer erfordern höherlegierte Werkstoffe, da die Korrosionsrate von niedriglegiertem Stahl zu hoch ist.
• Der Duplexstahl X2CrNiMo22-5-3 und der Superduplexstahl X2CrNiMoCuWN25-7-4 wurden aufgrund ihrer kritischen Anfälligkeit für örtliche Korrosion in Form von Loch- und Spaltkorrosion unter Betriebsbedingungen nicht als geeignet für geothermische Anwendungen in Geothermalwässern mit einer mit NDB und ORG vergleichbaren Zusammensetzung angesehen.
• Der superaustenitische Stahl X1CrNiMoCu32-28-7 eignet sich für ORG und salzarme Wässer. In NDB-Geothermalwasser wurde er bei 100 °C als geeignet angesehen. Jedoch schränkt seine Anfälligkeit für Spaltkorrosion seine Anwendbarkeit ein. Neben seiner guten Korrosionsbeständigkeit ist sein Repassivierungsverhalten für seine begrenzte Anwendbarkeit in Geothermalwässern mit niedrigem pH-Wert verantwortlich.
• Die Nickelbasislegierung NiCr23Mo16Al wurde als geeignet erachtet und stellt eine sichere Option für den Einsatz in geothermischen Anlagen dar, selbst wenn mit stark salzhaltigem Geothermalwasser gearbeitet wird.
Durch Auslagerungs- und elektrochemische Tests im Labor kann das Korrosionsverhalten verschiedener metallener Werkstoffe beurteilt werden. Aus den Versuchsergebnissen, die in verschiedenen synthetischen Geothermalwässern im Labor erzielt wurden, lassen sich die folgenden Schlussfolgerungen ziehen:
• Die Anfälligkeit für Spaltkorrosion wurde als wichtigster Aspekt für die Werkstoffqualifizierung ermittelt.
• Der niedriglegierte Stahl 25CrMo4 zeigte bei niedrigem Salzgehalt in MB-Geothermalwasser eine gleichmäßige Korrosion unterhalb der akzeptierten Schwelle von 0,3 mm/Jahr. Daher kann er als geeignet für geothermische Bedingungen mit niedrigem Salzgehalt angesehen werden, wie sie für MB getestet wurden. Es besteht keine Notwendigkeit, auf höherlegierte (teurere) Werkstoffe auszuweichen. Ein niedrigerer pH-Wert (wie bei LHD) führt zu Korrosionsraten oberhalb der akzeptablen Grenzwerte, so dass die niedriglegierten Werkstoffe nicht für Flüssigkeiten mit niedrigem pH-Wert geeignet sind.
• Stark salzhaltige Geothermalwässer erfordern höherlegierte Werkstoffe, da die Korrosionsrate von niedriglegiertem Stahl zu hoch ist.
• Der Duplexstahl X2CrNiMo22-5-3 und der Superduplexstahl X2CrNiMoCuWN25-7-4 wurden aufgrund ihrer kritischen Anfälligkeit für örtliche Korrosion in Form von Loch- und Spaltkorrosion unter Betriebsbedingungen nicht als geeignet für geothermische Anwendungen in Geothermalwässern mit einer mit NDB und ORG vergleichbaren Zusammensetzung angesehen.
• Der superaustenitische Stahl X1CrNiMoCu32-28-7 eignet sich für ORG und salzarme Wässer. In NDB-Geothermalwasser wurde er bei 100 °C als geeignet angesehen. Jedoch schränkt seine Anfälligkeit für Spaltkorrosion seine Anwendbarkeit ein. Neben seiner guten Korrosionsbeständigkeit ist sein Repassivierungsverhalten für seine begrenzte Anwendbarkeit in Geothermalwässern mit niedrigem pH-Wert verantwortlich.
• Die Nickelbasislegierung NiCr23Mo16Al wurde als geeignet erachtet und stellt eine sichere Option für den Einsatz in geothermischen Anlagen dar, selbst wenn mit stark salzhaltigem Geothermalwasser gearbeitet wird.
Polymers with intrinsic microporosity are promising candidates for the active separation layer in gas separation membranes. These polymers are characterized by a high permeability and reasonable permselectivity. The latter point is somehow surprising because for microporous systems a more Knudson-like diffusion is expected then a size dependent temperature activated sieving process. It was argued in the framework of a random gate model that molecular fluctuations on a time scale from ps to ns are responsible for the permselectivity.
Here series of polymers of intrinsic microporosity (PIMs) as well as microporous polynorbornenes with bulky Si side groups and a rigid backbone are considered. The polymers have different microporosity characterized by high BET surface area values.
First inelastic time-of-flight neutron scattering measurements were carried out to investigate the low frequency density of state (VDOS). The measured data show the characteristic low frequency excess contribution to the VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. It was found that the frequency of the maximum position of the Boson peak correlates with the BET surface area value.
Secondly elastic scans as well as quasielastic neutron scattering measurements by a combination of neutron time-of-flight and backscattering have been out. A low temperature relaxation process was found for both polymers. This process was assigned to the methyl group rotation. It was analysed in terms of a jump diffusion in a three-fold potential. The analysis of the dependence of the elastic incoherent structure factor on the scattering vector yields the number of methyl groups which might be immobilized.
The neutron scattering experiments were accompanied by fast scanning calorimetry and broadband dielectric investigations as well as atomistic molecular dynamic simulations.
Safety is a key parameter for the design and construction of buildings. The most widely used construction material to date is concrete that consists of about 15-20 wt.-% cement, which is responsible for the main concrete properties, i.e., strength and durability. Despite many standards regulating the quality of cement, at present, there exists no viable method to track the cement life cycle “from cradle to grave”. This led to an increasing interest in simple and robust methods for studying the processes and changes occurring during the life cycle of cement. In this context, we explored the applicability of fluorescence measurements which can be performed with relatively inexpensive and miniaturized instrumentation yet require robust optical probes which survive the harsh cement environment. Therefore, we developed a platform of lanthanide-based upconversion nanoparticles (UCNPs), consisting of a NaYF4 matrix doped with Yb3+ and Er3+ with sizes between 20 nm and 55 nm, which show characteristic multi-color emission patterns, composed of narrow bands of varying intensity in the ultraviolet, visible, near-infrared, and short-wave spectral region and examined their potential for cement probing and the non-invasive monitoring of the hydration processes occurring during cement formation.
UCNPs of different size and chemical composition were synthesized via a thermal decomposition approach under inert conditions. The tailor-made design of different emission patterns was achieved by tuning particle size and morphology, material composition, and particle surface chemistry in upscaleable syntheses. For cement probing, different types of UCNPs were added to cement and the evolution of the UCNP emission pattern was used to probe in-situ changes of physico-chemical parameters in the cementitious environment during hydration, utilizing a simple and portable custom-designed optical setup. The observed changes in the UCNP emission patterns are characteristic for a given particle size, surface chemistry, and cement composition. In addition to fluorescence measurements, conventional isothermal heat flow calorimetry was used to study the influence of UCNP addition on cement hydration kinetics. Subsequently, both sets of measurements were correlated. Our results underline the potential of our optical approach ad UCNPs for the non-invasive probing of cementitious systems and cement hydration. This can be also exploited for cutting-edge applications of construction materials such as 3D concrete printing.
Design and construction of a rainfall simulator to test metal runoff at atmospheric conditions
(2023)
A rainfall simulator was presented as an environmental assessment tool to quantify wash-off concentrations from metallic materials. It is part of the RUNOFF-project, which studies and re-assesses the durability of roofing and facade materials under current atmospheric conditions in Germany.
Studying building materials is important as they have a significant impact on achieving a variety of goals and targets within the sustainable developments goals (SDGs). The durability of materials is essential to reach sustainability. However, the durability of metallic materials is strongly depended on climate conditions, which have changed as a result of technical measures in industry, climate change and increasing urbanisation. In Germany at least, the data base is not up-to-date leading to prediction models regarding corrosion resistance and durability of metallic materials which can no longer be trusted and therefore need to be re-assessed and updated. Also, not only the demand for sustainable but also environmentally friendly building materials has increased dramatically. A number of construction materials produce chemical hazards, and therefore have negative impacts on water quality, soils health and ecosystems. To limit these impacts, environmental assessment methods and tools are needed to measure and quantify the inputs and outputs of building materials throughout their lifetime.
Polymeric membranes represent a cost- and energy-efficient solution for gas separation. Recently Polymers of Intrinsic Microporosity (PIMs) have been in a great interest because of their outstanding BET surface area larger than 700m2/g and pore size smaller than 1 nm. PIMs are a promising candidate in gas separation with high permeability and appealing selectivity due to their inefficient packing derived from a combination of ladder-like rigid segments with sites of contortion. However, it is recognized this class of polymers suffer from decrease in performance with time due to physical aging. The initial microporous structures approach a denser state via local chain rearrangements, leading to a dramatic reduction in permeability. As chain packing during film casting and physical aging are the key factors determine the performance in separation applications, characterization of the molecular mobility in these materials has been proved to provide valuable information. In recent research on PIM-1 the archetypal PIM, a molecular relaxation process with high activation energy together with a significant conductivity in the glassy state has been found and explained with the formation of local intermolecular agglomerates due to interaction of π-electrons in aromatic moieties of the polymer backbone. In this work, the dielectric behavior of the polymeric films and their response upon heating (aging) were measured by isothermal frequency scans during different heating/cooling cycles in a broad temperature range down to 133K for the first time. Multiple dielectric processes following Arrhenius behavior were observed. Local fluctuations, Maxwell-Wagner-Sillars (MWS) polarization and structural relaxations were discussed correlating to structural-properties of PIM-1. Up to now, no other work has studied the role of porosity and thermal history of PIM-1 film in dielectric processes. The goal is by eliminating thermal history and considering storing conditions provide better understanding on aging and plasticizing in high free volume glassy polymer PIM-1.
Especially now in times of the energy revolution, the demand for energy-efficient separation processes promotes the advancement of new high-performance materials for use as highly selective separation membranes. Polymers with intrinsic microporosity (PIMs) are of high interest in the field of gas separation membranes. Currently the application of PIMs for membrane technology is still restrained by their strong tendency to physical aging involving a significant loss of their good gas separation properties. Physical aging phenomenon is related to the molecular mobility of PIMs which was investigated by broadband dielectric spectroscopy (BDS) previously [1]. In this work, covalent phosphinine-based framework (Eto-CPSF) was used as a nanofiller (0-10 wt %) in a PIM-1 matrix to potentially enhance the gas transport properties and prevent physical aging. Since molecular mobility is a fundamental parameter determining gas transport as well as physical aging in such a material, our study includes dielectric investigations by BDS of pure PIM-1 and PIM-1/Eto-CPSF mixed matrix membranes to establish a correlation between molecular mobility and gas transport properties. In addition, gas permeability was determined by the time-lag method (0-10 bar pressure) at 35 °C for N2, O2, CH4 and CO2 for all MMMs.
The dielectric behavior of the polymeric films and their response upon heating were measured by isothermal frequency scans during different heating/cooling cycles in a broad temperature range up to 250 °C. Multiple dielectric processes following Arrhenius behavior were observed. Local fluctuations, Maxwell-Wagner-Sillars (MWS) polarization and structural relaxations were discussed correlating to structural-properties of PIM-1. As main result for MMMs, the permeability of PIM-1 for CH4 and CO2 gases were increased significantly with only 5 wt% of nanofiller within the polymer matrix. However, this is not observed for Eto-CPSF concentrations higher than ca. 7 wt% probably due to a microphase separated morphology of the nanocomposite system. Furthermore, the permselectivity of membranes for pair gases O2/N2 and CO2/N2 show enhancement up to a concentration of about 7 wt% Eto-CPSF filler.
The chapter gives a brief introduction to (nano)compositecomposite materials having the focus on polymer-based nanocomposites. The different dimensionalities of nanoparticles are introduced, along with their distribution in the matrix.
Different application fields of polymer-based nanocomposites, like flame retardancy, filled rubbers, nanofilled thermosets and thermoplastics, separation membranes and nanodielectrics, are considered in greater detail.
Sehr geehrte Damen und Herren,
liebe Leserinnen und Leser,
bereits im ersten Band der N.i.Ke. Schriftenreihe des Netzwerks zur interdisziplinären Kulturerhaltung hatte ich angeführt, dass bei der Untersuchung von kulturellen Artefakten naturwissenschaftliche Untersuchungsmethoden zunehmend an Bedeutung gewinnen, sie eigentlich unverzichtbar geworden sind.
Ein besonders einprägsames Beispiel dieser fächerübergreifenden Zusammenarbeit zwischen Geisteswissenschaften, Naturwissenschaften und Restaurierungswissenschaften war die Ausstellung Johannes Vermeer. Vom Innehalten, die in diesem Jahr in der Gemäldegalerie Alter Meister in den staatlichen Kunstsammlungen Dresden gezeigt wurde. Eigens für diese Ausstellung wurde das Gemälde Brieflesendes Mädchen am offenen Fenster einer grundlegenden Restaurierung unterzogen. Diese Restaurierung diente jedoch nicht nur der Reparatur des Bildes. Um sich dem ursprünglichen Zustand des Gemäldes zwischen 1657 und 1659 anzunähern, wurden später hinzugefügte Malschichten großflächig abgenommen. Möglich wurde dies durch unterschiedliche, bildgebende materialwissenschaftliche Untersuchungen im Vorfeld, welche die wissenschaftlichen Grundlagen für die Diskussion über den weiteren Umgang mit der Lesenden schufen.
Materialanalytische Verfahren wurden und werden ständig weiterentwickelt und optimiert. Sei es, um aus einer Vielzahl von Einzelmessungen ein Gesamtbild zu erstellen, oder die Größe einer Probenentnahme so zu reduzieren, dass von einer „minimal-invasiven“ oder „quasi nicht-invasiven“ Untersuchung ausgegangen werden kann. Nun feiert die Bundesanstalt für Materialforschung und -prüfung, zusammen mit ihren Vorgängerinstitutionen, den königlichen Versuchsanstalten, in diesem Jahr ihren einhundertfünfzigsten Geburtstag. Sie blickt damit auf eine lange Tradition materialwissenschaftlicher Analysen zurück, an deren Beginn beispielsweise die metallographischen Untersuchungen von Adolf Martens stehen. Derartige Untersuchungen bilden auch heute noch einen wesentlichen Bestandteil archäometallurgischer Forschung. Die Historie bzw. die Weiterentwicklung der Methodik lässt sich hier besonders gut nachzeichnen. Jedoch blicken auch Verfahren zur Charakterisierung weiterer Werkstoffe, wie Glas, Keramik, oder organischer Materialien auf eine lange Geschichte zurück.
Die in diesem Band der N.i.Ke.-Schriftenreihe präsentierten Beiträge dokumentieren einerseits aktuelle Forschungsarbeiten, die erst in diesem Jahr in entsprechenden Fachjournalen publiziert wurden, andererseits liegen einige der Arbeiten bereits 50 Jahre zurück. Sie bekunden damit nicht nur die materialtechnologische und historische Bandbreite der Projekte, sondern offenbaren die Vielfältigkeit kulturhistorischer oder restauratorischer Fragestellungen, zu deren Beantwortung natur- und materialwissenschaftliche Forschung wesentliche Beiträge liefern können.
Ich bedanke mich bei allen Kolleginnen und Kollegen, die zur Erstellung dieser dritten Ausgabe der N.i.Ke. Schriftenreihe des Netzwerks zur interdisziplinären Kulturerhaltung beigetragen haben. Ihre Aufsätze ermöglichen den Blick in die Vielfältigkeit materialwissenschaftlicher Untersuchungen im Bereich Kunst- und Kulturgut. Ich wünsche Ihnen viel Spaß auf dieser kleinen Zeitreise.
We report dielectric and calorimetric studies on metathesis and addition-type polytricyclononenes, both based on the same monomer bearing three pendant OSiMe3 groups. For the addition-type polymer, dielectric spectroscopy reveals a β*-process related to the microporosity, whereas for its metathesis counterpart, the segmental dynamics manifests as an α-process related to a glass transition. Besides active dielectric processes, a significant conductivity contribution is detected for both samples which for the microporous additiontype polymer is three orders of magnitude greater than for the metathesis polymer. The broadband dielectric spectroscopy is complemented by detailed calorimetric investigations, comprising DSC, FSC, and TMDSC. The calorimetric methods detected the glass transition for the metathesis polymer in agreement with the observed dielectric α-process. Furthermore, the already reported gas transport properties for both polymers are compared, setting them in correlation with the observed molecular mobility and conductivity behavior. The discussed results reflect significant differences in molecular mobility of the two polymers affecting the appearance of microporosity which strongly determines the gas transport properties.
Stone deterioration is the result of a complex interaction of external physical, chemical and biological forces with the mineralogical-petrophysical properties of the stone. With a better understanding of how these properties are linked to material behavior and durability, more effective measures for stone conservation can be developed. Studying these interactions in tuff is particularly complex due to the naturally high heterogeneity of tuff rocks.
The first aim of a current research project is to combine the results of recent and older studies on tuff deterioration. Furthermore, the literature overview is complemented by our own investigation of Weibern and Ettringen tuff, with a focus on pore structure characteristics.
The aim of the work presented was the evaluation of corrosion resistance
of various materials in geothermal Waters as a base to create a catalogue of suitable materials for applications in (not only) German geothermal power plants.
Users shall be enabled to have a basis for designing such facilities. High alloyed corrosion resistant alloys are suitable and do not cause copper or lead deposition. They shall be chosen for future design of the piping system, either in massive or in cladded form, if crevices formation with non-metallic materials can be prevented!
Alkali-activated materials have been repeatedly reported to exhibit high acid resistance, but no generally accepted hypothesis regarding the underlying mechanisms has emerged yet. To contribute to this issue, K-waterglass-activated metakaolin specimens, with and without the addition of CuSO4·5H2O in the starting mix, were exposed to either a chemically aggressive sewer environment (mortars) or sulfuric acid (pastes). The mode of copper incorporation in the materials and the formation of copper phases in the corroded layers were studied by XANES at the Cu K-edge, and 29Si, 27Al and 1H MAS NMR was employed to understand the processes during acid attack. Copper was found as a spertiniite-like phase in the as-cured materials, while in the deterioration layers of the pastes it was present as copper sulfate. In the corroded regions of the mortars, unequivocal identification of Cu phases was not possible, but the results were reconcilable with the presence of copper carbonate hydroxide. The solid-state NMR results revealed virtually complete dissolution of the K-A-S-H gel and the formation of silica gel, interpreted to be a central mechanism determining the acid resistance. No significant differences between the microstructural alterations of the pastes with and without Cu addition on (chemical) sulfuric acid attack were observed.
Polymers with intrinsic microporosity are promising candidates for the active separation layer in green gas separation membranes and as active materials for electronic applicatons. Here, by means of inelastic neutron scattering, the vibrational density of states (VDOS) and the molecular mobility were investigated for PIM-1, the prototypical polymer with intrinsic microporosity. The results are compared to data measured for a more conventional high-performance polyimide used in gas separation membranes (Matrimid).
The measured data show the characteristic low frequency excess contribution to the VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. In comparison to the Boson peak of Matrimid, that of PIM-1 is shifted to lower frequencies. This shift is discussed considering the microporous, sponge-like structure of PIM-1 as providing a higher compressibility at the molecular scale than for conventional polymers.
Elastic fixed window scans were measured on a neutron backscattering spectrometer to have an overview about the molecular dynamics at a time scale of ca. 1 ns. The temperature dependence of the estimated mean squared displacement shows a step-like increase in the temperature range from 100 K to 250 K indicating the onset of some molecular mobility. The nature of this motional process was analysed in detail by quasielastic neutron scattering combining Time-of-Flight and backscattering where the data are discussed with regard to both the q- and the temperature dependence.
Polymers of intrinsic microporosity (PIMs) have recently emerged as novel materials for a broad range of high-performance applications from gas separation to electronic devices. The very rigid, contorted polymer chains show only limited molecular mobility and therefore pack inefficiently giving rise to intrinsic microporosity with pore sizes generally smaller than 1 nm resulting in BET surface areas larger than 700 m2/g. Using conventional thermal analysis techniques, no glass transition temperature (Tg) of PIMs could be unambiguously detected up to now. Employing fast scanning calorimetry (FSC) based on a one chip sensor, decoupling the time scales responsible for the glass transition and the thermal decomposition is a reliable strategy to overcome this limitation. The FSC device is capable to heat and cool a small sample (ng-range) with ultrafast rates of several ten thousand K/s. Evidence of a glass transition is obtained for a series of PIMs with different chain rigidities. Local small-scale fluctuations are held responsible for the glass transition of highly rigid PIMs rather than segmental motions as in conventional polymers.
Organic/inorganic mixtures were prepared from ordinary Portland cement (OPC), water (w/c 0.22), a fluorescent dye in aqueous solution (stable at alkaline pH; BAM-I), and two different comb shape polycarboxylates (PCEs), i.e., high charge (PCE-HC) and low charge (PCE-LC), respectively. Rheological and calorimetric measurements were performed prior to optical studies in order to select PCE concentrations. Absorption and fluorescence spectroscopy of the system OPC + BAM-I (CBAM-I) revealed maxima of dye BAM-I located at 645 nm and 663 nm, respectively. In presence of PCE-HC and PCE-LC, these mixtures displayed a small red shift in reflectance and a faster decrease in intensity compared to studies with CBAM-I; however, only slight differences were observed between the different PCEs. With time, all systems exhibited a decrease in intensity of BAM-I in absorption/reflectance and emission. This could be caused by dye adsorption and possibly decomposition when in contact with cement particles or hydration products.
Einkomponentige alkaliaktivierte Bindemittel (AAB), d. h. AAB, bei denen der Aktivator als Feststoff im Bindemittel vorliegt, weisen Vorteile hinsichtlich der praktischen Anwendung im Bauwesen gegenüber konventionellen AAB auf. Einkomponentige AAB lassen sich als Gemische aus reaktiver Silica und Natriumaluminat herstellen, wobei die Reaktionsprodukte von der eingesetzten Silica und den Verhältnissen Na2O/Al2O3/SiO2/H2O abhängen: Während Mikrosilica und ähnliche Reststoffe zu zeolithreichen Produkten führen, erhält man aus Reisschalenasche vollständig amorphe Gele (sog. «Geopolymere »). Mörtel auf Basis solcher Bindemittel entsprechen den Anforderungen von DIN 19573:2016-03 hinsichtlich des Widerstands gegen Schwefelsäureangriff (Prüfung bei pH = 1 für 70 d) und sind damit potentiell als Reparatursysteme für Abwasserinfrastruktur geeignet. Untersuchungen mittels 29Si-MAS-NMR und 1H-29Si-Kreuzpolarisations(CP)-MAS-NMR sowie REM-Aufnahmen von erhärteten und dem Schwefelsäureangriff ausgesetzten AAB zeigen, dass der hohe Säurewiderstand v. a. auf die Fällung von Silicagel an der Grenzfläche Mörtel/Säure zurückzuführen ist, wodurch der Korrosionsfortschritt in darunterliegenden Schichten verlangsamt wird.
Polymers with intrinsic microporosity are promising candidates for the active separation layer in gas separation membranes. Here, by means of inelastic neutron scattering, the vibrational density of states (VDOS) and the molecular mobility were investigated for PIM-1, the prototypical polymer with intrinsic microporosity. The results are compared to data measured for a more conventional high-performance polyimide used in gas separation membranes (Matrimid).
The measured data show the characteristic low frequency excess contribution to the VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. In comparison to the Boson peak of Matrimid, that of PIM-1 is shifted to lower frequencies. This shift is discussed considering the microporous, sponge-like structure of PIM-1 as providing a higher compressibility at the molecular scale than for conventional polymers.
Elastic fixed window scans were measured on a neutron backscattering spectrometer to have an overview about the molecular dynamics at a time scale of ca. 1 ns. The temperature dependence of the estimated mean squared displacement shows a step-like increase in the temperature range from 100 K to 250 K indicating the onset of some molecular mobility. The nature of this motional process was analyzed in detail by quasielastic neutron scattering combining Time-of-Flight and backscattering where the data are discussed with regard to both the q- and the temperature dependence.
Einkomponentige alkaliaktivierte Bindemittel (AAB), d. h. AAB, bei denen der Aktivator als Feststoff im Bindemittel vorliegt, weisen Vorteile hinsichtlich der praktischen Anwendung im Bauwesen gegenüber konventionellen AAB auf. Einkomponentige AAB lassen sich als Gemische aus reaktiver Silica und Natriumaluminat herstellen, wobei die Reaktionsprodukte von der eingesetzten Silica und den Verhältnissen Na2O/Al2O3/SiO2/H2O abhängen: Während Mikrosilica und ähnliche Reststoffe zu zeolithreichen Produkten führen, erhält man aus Reisschalenasche vollständig amorphe Gele (sog. «Geopolymere»). Mörtel auf Basis solcher Bindemittel entsprechen den Anforderungen von DIN 19573:2016-03 hinsichtlich des Widerstands gegen Schwefelsäureangriff (Prüfung bei pH = 1 für 70 d) und sind damit potentiell als Reparatursysteme für Abwasserinfrastruktur geeignet. Untersuchungen mittels 29Si-MAS-NMR und 1H-29Si-Kreuzpolarisations(CP)-MAS-NMR sowie REM-Aufnahmen von erhärteten und dem Schwefelsäureangriff ausgesetzten AAB zeigen, dass der hohe Säurewiderstand v. a. auf die Fällung von Silicagel an der Grenzfläche Mörtel/Säure zurückzuführen ist, wodurch der Korrosionsfortschritt in darunterliegenden Schichten verlangsamt wird.
The presence of polycarboxylate ether (PCE) based superplasticizers (SPs) has enormous influence on the early hydration of cement. C3A as the most reactive phase of Portland cement plays a significant role in early hydration reactions and affects the rheological performance. Therefore, this paper presents experimental results about the influence of delayed addition of PCEs on the Hydration of cement and C3A-gypsum pastes investigated by isothermal heat flow calorimetry. Complementary in-situ XRD was carried out on C3A pastes to analyze hydration and phase changes related to the addition of PCE.
Cement pastes with a delayed addition of PCE showed less Retardation compared to simultaneous addition. The alteration caused by PCE is much more pronounced for C3A-gypsum mixes. With a delayed addition of SP, the hydration of C3A is less retarded or even accelerated. It is obvious that there is less retardation the later the addition of SP. Furthermore, the PCE alter the hydration of C3A when added delayed and exhibit changes in kinetics and hydration rates. XRD results showed that more C3A is dissolved in the presence of PCE. Also, the gypsum depletion occurs earlier in the presence of PCE and even faster with delayed addition. Without PCE AFm starts to form just after the gypsum depletion. However, in the presence of PCE AFm already starts to form at the beginning of the hydration. Due to the faster gypsum depletion in the presence of PCE, also the transformation from ettringite into AFm begins earlier, but takes longer as without SP.
The presence of polycarboxylate ether (PCE) based superplasticizers (SPs) has enormous influence on the early hydration of cement. C3A as the most reactive phase of Portland cement plays a significant role in early hydration reactions and affects the rheological performance. Therefore, this talk presents experimental results about the influence of delayed addition of PCEs on the Hydration of alite and C3A-gypsum pastes investigated by isothermal heat flow calorimetry. Complementary in-situ XRD was carried out on C3S and C3A-gypsum pastes to analyze hydration and phase changes related to the addition of PCE. Cement pastes with a delayed addition of PCE showed less retardation compared to simultaneous addition. The alteration caused by PCE is much more pronounced for C3A-gypsum mixes. With a delayed addition of SP, the hydration of C3A is less retarded or even accelerated. It is obvious that there is less retardation the later the addition of SP. Furthermore, the PCE alter the hydration of C3A when added delayed and exhibit changes in kinetics and Hydration rates. XRD results showed that more C3A is dissolved in the presence of PCE. Also, the gypsum depletion occurs earlier in the presence of PCE and even faster with delayed addition. Without PCE AFm starts to form just after the gypsum depletion. However, in the presence of PCE AFm already starts to form at the beginning of the hydration. Due to the faster gypsum depletion in the presence of PCE, also the transformation from ettringite into AFm begins earlier, but takes longer as without SP.
A central challenge to ensure the sustainable production and use of nanotechnologies is to understand and effectively control the risks along the industrial innovation value chain. Knowledge about nanotechnology processes and nanosafety issues (hazards, fate, risk...) is growing rapidly but the effective use of this knowledge for risk management by market actors is lagging behind.
EC4SafeNano (European Centre for Risk Management and Safe Innovation in Nanomaterials and Nanotechnologies) promotes a harmonized vision of expertise in risk assessment and management for the public and private sectors to enable the safe development and commercialization of nanotechnology.
EC4SafeNano is operated together by major European risk institutes with the support of numerous associated partners, gathering all stakeholders involved in Nanomaterials and Nanotechnologies (regulators, industry, society, research, service providers...).
In a case study the surface chemical transformations upon 2 different ageing procedures (long-term UV irradiation or swimming pool water) of a representative set of titanium dioxide nanoparticles has been investigated. The materials have been analyzed by various analytical techniques. Each method addresses different aspects of the complex endpoint surface chemistry. The multi technique approach allows evaluation of the capabilities and limitations of the applied methods regarding their suitability to address the endpoint surface chemistry and their sensitivity to identify even small surface chemical transformations.
Results:
- To obtain a comprehensive picture, it is insufficient to concentrate on a single analysis technique.
- By using time-of-flight secondary ion mass spectrometry (ToF-SIMS) in combination with principal component analysis (PCA) it was possible to identify even subtle changes in the surface chemistry of the investigated materials.
- A general trend that was observed for the UV-aged samples is the decrease of organic material on the nanomaterial surface.
This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 723623.
Polymers with intrinsic microporosity are promising candidates for the active separation layer in gas separation membranes. Here, by means of inelastic neutron scattering, the vibrational density of states (VDOS) and the molecular mobility were investigated for PIM-1, the prototypical polymer with intrinsic microporosity. The results are compared to data measured for a more conventional high-performance polyimide used in gas separation membranes (Matrimid).
The measured data show the characteristic low frequency excess contribution to the VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. In comparison to the Boson peak of Matrimid, that of PIM-1 is shifted to lower frequencies. This shift is discussed considering the microporous, sponge-like structure of PIM-1 as providing a higher compressibility at the molecular scale than for conventional polymers.
Elastic fixed window scans were measured on a neutron backscattering spectrometer to have an overview about the molecular dynamics at a time scale of ca. 1 ns. The temperature dependence of the estimated mean squared displacement shows a step-like increase in the temperature range from 100 K to 250 K indicating the onset of some molecular mobility. The nature of this motional process was analyzed in detail by quasielastic neutron scattering combining Time-of-Flight and backscattering where the data are discussed with regard to both the q- and the temperature dependence.
Materials with a high acid resistance are required in different important infrastructures. Examples include repair systems for sewer structures, where biogenic sulfuric acid corrosion is the major degradation mechanism. Low-calcium alkali-activated materials (AAMs) have been repeatedly observed to exhibit high acid resistance. However, the reasons for the high acid resistance of these materials were not fully under¬stood until recently, and the use of highly alkaline activator solutions to produce AAMs appears to hamper their commercial uptake. These issues have been tackled by characterising one-part AAMs and studying their alteration when exposed to sulfuric acid.
One-part AAMs were synthesized by mixing blends of solid silica and sodium aluminate with water, and subsequent curing at 60–80 °C. Acid resistance testing was performed according to DIN 19573, i.e. exposure to sulfuric acid at pH = 1 for 70 days. Characterisation of the cured and the acid-exposed materials was done by XRD, ATR-FTIR, SEM as well as 29Si, 27Al and 1H MAS NMR spectroscopy, including cross-polarisation and double-resonance methods.
Materials synthesized from industrial silicas were gel-zeolite composites, containing a substantial amount of unreacted ‘excess’ silica, while materials synthesized from rice husk ash were fully amorphous, containing ‘excess’ hydrous alumina. The sulfuric acid resistance of mortars based on these binders conformed to the requirements of DIN 19573 for sewer repair applications. The high acid resistance was caused by precipitation of silica gel at the mortar–solution interface, inhibiting further degradation. The presence of alumina gel may inhibit bacterial activity, potentially further improving performance in sewer environments.
The phase assemblage of silica/sodium aluminate-based one-part AAMs can be adjusted via choice of the silica starting material. Properly designed materials exhibit excellent acid resistance, caused by precipi¬tation of silica gel which protects subjacent regions, and they may also inhibit bacterial activity.
In recent years superglassy polymers exhibiting intrinsic microporosity established a new perspective for a number of applications, especially for gas separation membranes as These polymers Combine extremely high permeabilities with attractive selectivities. The essential factor governing the structure Formation in the solid film or layer is either a contorted rigid Backbone (polymers of intrinsic microporosity - PIMs) or extremely bulky side groups (polynorbornenes and polytricyclonenenes).
For a deeper understanding of both types of such high-Performance polymers for gas separation membranes and their further development broadband dielectric spectroscopy (BDS) can provide a substantial contribution.
BDS addresses molecular relaxations characterizing the dynamics of the solid polymer as a major factor determining the gas transport properties but also the physical aging behavior which is an essential issue for such polymers.
BDS is applied on PIMs where fluctuations of molecular dipoles connected to the backbone can be directly monitored. Furthermore, also polynorbornenes were investigated which carry no dipole moment in their repeat unit - the high resolution of modern equipment allows for the detailed analysis also for very small dielectric losses originating from partially oxidized moieties or marginal catalyst residues.
Additionally, from interfacial polarization phenomena, such as Maxwell-Wagner-Sillars (MWS) polarization due to blocking of charge carriers at internal interfacial boundaries on a mesoscopic length scale, valuable information on the intrinsic microporosity and its changes induced by physical aging can be obtained.
Finally, also conductivity can be characterized in detail in such polymeric systems revealing contributions of interactions of aromatic moieties (π-π-stacking) or the drift motion of charge carriers. These features also determine the structure formation in the solid state.
High performance polymers of intrinsic microporosity (PIMs) have emerged as novel materials with broad applications from gas separation to electronic devices. Sufficiently rigid, even contorted polymer chains show only limited molecular mobility, therefore undergo inefficient packing and give rise to intrinsic microporosity with pore size generally smaller than 1 nm and BET surface areas larger than 700 m2/g. Further performance optimization and long-term stability of devices incorporating PIMs rely on our understanding of structure-processing-property relationships and physical aging, in which glass transition plays a key role. Up to now no glass transition temperature (Tg) of PIMs could be detected with conventional thermal analysis techniques before degradation. Decoupling the time scales responsible for the glass transition and the thermal decomposition is a reliable strategy to overcome this. This was achieved by employing fast scanning calorimetry (FSC) based on a chip sensor, which is capable to heat and cool a small sample (ng-range) with ultrafast rates of several ten thousand K/s. FSC provides definitive evidence of glass transition of a series of PIMs with a special consideration on the chain rigidity. The determined glass transition temperature of these PIMs follows the order of the rigidity of their backbone structures. FSC provides the first clear-cut experimental evidence of the glass transition of PIM-EA-TB with a Tg of 663 K, PIM-1 of 644 K and PIM-DMDPH-TB of 630 K at a heating rate of 1Χ104 K/s. Local fluctuations are featured in glass transition of highly rigid PIMs. As conformational changes are prevented by the backbone rigidity, the glass transition must rather be assigned to local small scale fluctuations.
Polymeric membranes represent a low-cost, energy efficient solution for gas separation. Recently polymers of intrinsic microporosity (PIMs) have emerged as prestigious membrane materials featuring a large concentration of pores smaller than 1 nm, a BET surface area larger than 700 m2/g and high gas permeability and selectivity. Unusual chain structure combining rigid segments with sites of contortion gives rise to the intrinsic microporosity. However, this novel class of glassy polymers are prone to pronounced physical aging. The initial microporous structures approach a denser state via local small scale fluctuataions, leading to a dramatic reduction in the gas permeabilities. For the first time, dielectric relaxation spectroscopy with state-of-the-art high-resolution analyzers was employed to investigate three representative PIMs with a systematic change in chain rigidity: PIM-EA-TB 〉 PIM-1 〉 PIM-MDPH-TB. The molecular mobility, the charge transport and their response upon heating (aging) in the polymers were measured in a broad temperature range through isothermal frequency scans during different heating / cooling cycles. Multiple dielectric processes following Arrhenius behavior were observed for the investigated polymers. Local fluctuations, Maxwell-Wagner-Sillars (MWS) polarization and structural relaxation phenomena were discussed and attempted to be correlated with the structural features of PIMs. Moreover, all PIMs showed conductivity in the glassy state. The significant increase in the conductivity with increasing temperature far below the glass transition temperature of PIMs is explained in terms of the loosely packed microporous structure and the formation of local intermolecular agglomerates due to interaction of π-electrons in aromatic moieties of the polymer backbone.
Nanomaterials are a relatively new class of materials for which a regulatory framework still has to be established and regulators require comprehensive datasets of well characterized nanomaterials for the implementation. Especially information about the surface chemistry of nanoparticles is crucial, since it largely determines their biological and environmental fate. How the surface chemistry changes under relevant ageing conditions is of particular interest, because exposure will normally occur not to the pristine material but to a nanoform that underwent some kind of transformation.
In this talk, first a short overview about the contributions of division 6.1 to multiple European-funded projects will be presented, in which surface analytical techniques are used to improve the physical-chemical characterization of nanomaterials. Secondly, a study investigating the surface-chemical transformations of a representative set of titanium dioxide nanoparticles is discussed in more detail. The ageing has partly been performed at the BAM division 7.5, and the surface chemistry was analyzed using time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS). By analyzing the complex mass spectra with principal component analysis (PCA), it was possible to identify even subtle changes that occur upon ageing.
The presence of polycarboxylate ether (PCE) based superplasticizers (SPs) has an enormous influence on the early hydration of cement. The hydration is retarded and the timing of formation and the morphology of hydrates is affected. This short paper presents experimental results about the influence of delayed addition time of PCE SPs on hydration of cement and alite pastes, investigated by isothermal heat flow calorimetry. For cement as well as for alite pastes the hydration is retarded with SP, whereby the high charge PCE has a stronger retarding effect than the low charge PCE. The retardation caused by PCE is much more pronounced for alite than for cement mixes. If PCE is added later to the mix, the induction period is shortened and the hydration is accelerated compared to simultaneous addition. This applies for cement and alite pastes. With delayed PCE addition the alite shows a clearly less retarded setting and main hydration than after simultaneous addition. It is obvious that for alite pastes there is less retardation the later the addition of SP.
The paper presents rheometric results and hydration curves for cementitious systems based on cement mixed with different aqueous phases at solid volume fraction of = 0.45. The varied aqueous phases were deionized water, limewater, the filter residue of a cement paste mixed at w/c = 2.0, and the filtrate of cement paste at solid volume fraction of 0.45. Each cementitious system provided different amounts and sizes of particles formed in the aqueous phase. The pastes were observed with and without polycarboxylate ether based superplasticizer. It was observed that the presence of particles causes higher PCE saturation dosages to achieve a minimum value, but the minimum value is only affected in the case of large particles. In all cases with and without PCE, the presence of small particles causes increased plastic viscosity. In addition, with decreased number and size of hydrates in the aqueous phase the hydration was retarded, which was specifically pronounced in the presence of PCE
The state of fresh concrete is predominantly determined by the rheological properties of the cement paste. In order to control performance spectra and requirements of novel concretes and to better understand macroscopic phenomena, comprehensive knowledge of the material behavior of fresh cement suspensions as well as of the complex relationships of mechanisms at the nano and micro scale are necessary. This work focuses on micro and nano rheology of suspensions of cementitious model systems and the influence of polycarboxylate-based admixtures on the rheology. The phenomena are driven by multiple parameters such as adsorption and particle interactions. Hence, the first part examines the interaction between polycarboxylate ether (PCE) and synthesized clinker phases and hydration products as model systems with regard to early hydration products.
The presence of polycarboxylate ether (PCE) based superplasticizers (SPs) has an enormous influence on the early hydration of cement. Therefore, the talk presents first experimental results about the influence of a delayed addition time of PCE SPs on the hydration of cement and tricalcium aluminate (C3A) pastes, investigated by isothermal heat flow calorimetry and in-situ XRD.
The presence of polycarboxylate ether (PCE) based superplasticizers (SPs) has an enormous influence on the early hydration of cement. The hydration is retarded and the timing of formation and the morphology of hydrates is affected. This short paper presents experimental results about the influence of delayed Addition time of PCE SPs on hydration of cement and tricalcium aluminate (C3A) pastes, investigated by isothermal heat flow calorimetry. For cement pastes the hydration is retarded with SP, whereby the high charge PCE has a stronger retarding effect than the low charge PCE. With delayed PCE addition the cement shows a less retarded setting than with simultaneous addition. The alteration caused by PCE is much more pronounced for C3A and gypsum mixes than for cement. If the SP is added simultaneous, the exothermic peak of C3A is retarded. However, with delayed addition of SP the hydration is shortened, the gypsum depletion is fastened and the exothermic peak occurs less retarded or even accelerated compared to simultaneous addition. It is obvious that for C3A pastes there is less retardation the later the Addition of SP. Furthermore, the PCE alter the hydration of C3A when added delayed and exhibit changes in kinetics and hydration rates. The rate of reaction in the second stage is lower, discernible in decreased slopes and broader peaks. Besides this, a distinct ramp in the C3A heat flow curves within the first stage of C3A hydration occurs for all pastes with delayed addition of SP, which suggests an accelerated ettringite formation.
Die Rheologie von fließfähigen zementären Systemen mit Fließmitteln wird durch eine Vielzahl parallel stattfindender Effekte beeinflusst. Zu diesen Effekten zählen Wechselwirkungen zwischen den Polymeren und Ionen in der Porenlösung, frühe Phasenbildung, zeitabhängige und kompetitive Adsorption zwischen anionischen Polymeren und Sulfationen, Bildung von Phasen in der Porenlösung sowie Morphologieänderungen an Partikeloberflächen. Die frühe Hydratation von Zement, die durch Lösungs- und Fällungsprozesse angetrieben wird, beeinflusst diese Effekte erheblich. Das permanente Ungleichgewicht der Porenlösung führt zu Veränderungen der Partikeloberflächen, welches widerum zur Folge hat, dass rheometrische Messungen dieser Zementleime anfällig für Streuungen sind. Um die Einflüsse aus der Zementhydratation zu minimieren, wurden die rheometrischen Untersuchungen mit Zement in Wasser, wässriger Phase von Zementleim bzw. mit vorhydratisiertem Zement durchgeführt. Zusätzlich wurden die gleichen Systeme mit Zugabe von Polycarboxylatethern untersucht.
Die Ergebnisse zeigen, dass die Leime mit Wasser niedrigere Werte für Fließgrenze und plastische Viskosität aufweisen, als die Systeme mit der wässrigen Phase von Zementleim. Während die Polymere eine Verminderung der Fließgrenze zur Folge hatte, war die Wirkung von Polymeren auf die plastische Viskosität vernachlässigbar. Zusätzlich wurde die frühe Hydratation unter Verwendung von Wärmeflusskalorimetrie, Rasterelektronenmikroskopie und Nadeleindringtiefe beobachtet.
Die Rheologie von fließfähigen zementären Systemen mit Fließmitteln wird durch eine Vielzahl parallel stattfindender Effekte beeinflusst. Zu diesen Effekten zählen Wechselwirkungen zwischen den Polymeren und Ionen in der Porenlösung, frühe Phasenbildung, zeitabhängige und kompetitive Adsorption zwischen anionischen Polymeren und Sulfationen, Bildung von Phasen in der Porenlösung sowie Morphologieänderungen an Partikeloberflächen. Die frühe Hydratation von Zement, die durch Lösungs- und Fällungsprozesse angetrieben wird, beeinflusst diese Effekte erheblich. Das permanente Ungleichgewicht der Porenlösung führt zu Veränderungen der Partikeloberflächen, welches widerum zur Folge hat, dass rheometrische Messungen dieser Zementleime anfällig für Streuungen sind. Um die Einflüsse aus der Zementhydratation zu minimieren, wurden die rheometrischen Untersuchungen mit Zement in Porenlösung durchgeführt. Die Experimente wurden mit verschiedenen Feststoffvolumenfraktionen durchgeführt und mit den Ergebnissen identischer Systeme mit Wasser anstelle von Porenlösung verglichen. Zusätzlich wurden die gleichen Systeme mit Zugabe von Polycarboxylatethern untersucht.
Die Ergebnisse zeigen, dass die Leime mit Wasser niedrigere Werte für Fließgrenze und plastische Viskosität aufweisen, als die Systeme mit Porenlösung. Während die Polymere eine Verminderung der Fließgrenze zur Folge hatte, war die Wirkung von Polymeren auf die plastische Viskosität vernachlässigbar. Zusätzlich wurde die frühe Hydratation unter Verwendung von Wärmeflusskalorimetrie, Rasterelektronenmikroskopie und Nadeleindringtiefe beobachtet.
Polymers with intrinsic microporosity are promising candidates for the active separation layer in gas separation membranes. Here, by means of inelastic neutron scattering, the vibrational density of states (VDOS) and the molecular mobility were investigated for PIM-1, the prototypical polymer with intrinsic microporosity. The results are compared to data measured for a more conventional high-performance polyimide used in gas separation membranes (Matrimid).
The measured data show the characteristic low frequency excess contribution to the VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. In comparison to the Boson peak of Matrimid, that of PIM-1 is shifted to lower frequencies. This shift is discussed considering the microporous, sponge-like structure of PIM-1 as providing a higher compressibility at the molecular scale than for conventional polymers.
Elastic fixed window scans were measured on a neutron backscattering spectrometer to have an overview about the molecular dynamics at a time scale of ca. 1 ns. The temperature dependence of the estimated mean squared displacement shows a step-like increase in the temperature range from 100 K to 250 K indicating the onset of some molecular mobility. The nature of this motional process was analyzed in detail by quasielastic neutron scattering where the data are discussed with regard to both the q- and the temperature dependence.
Die Bundesanstalt für Materialforschung und -prüfung (BAM) ist eine Ressortforschungseinrichtung, die zum Schutz von Mensch, Umwelt und Sachgüter, forscht, prüft und berät. Im Fokus aller Tätigkeiten in der Materialwissenschaft, der Werkstofftechnik und der Chemie steht dabei die technische Sicherheit von Produkten und Prozessen. Dazu werden Substanzen, Werkstoffe, Bauteile, Komponenten und Anlagen sowie natürliche und technische Systeme erforscht und auf sicheren Umgang oder Betrieb geprüft und bewertet. Schwerpunkt des Vortrages sind multimodale Polymeranalytik, nanoskalige Sensormaterialien und die Charakterisierung von technischen Eigenschaften von Polymeren sowie ihre Alterung und Umweltrelevanz.
One-part geopolymers (OPGs) are a sort of alkali-activated materials (AAMs) which production avoids the use of highly-alkaline activator-solutions and contributes to a better acceptance of alternative mineral binders in terms of safety-related and economic aspects. In the present contribution OPGs were synthesized by blending silica sources (two industrial silicas and two biogenic silicas) with sodium aluminate and only water must be added to initiate the hardening, i.e. mixing is performed in the same way as for conventional Portland cements. The OPGs were characterized by XRD, and SEM and the degrees of reaction of the silicas were determined by a chemical dissolution method.
The industrial silicas led to the formation of geopolymer-zeolite composites, that contained, besides geopolymeric gel, crystalline tectosilicates (e.g. zeolite A and hydrosodalite) and depending on the starting composition also unreacted silica. The biogenic silicas provided a higher reactivity and avoided the formation of crystallite by-products. The differences in the microstructures caused differences in the mechanical strength of the specimens.
The treatment of the OPG composites at moderate elevated temperatures revealed promising behavior on thermal dehydration in terms of shrinkage and residual strength up to 700 °C. Above 700 °C sintering and partial melting occurred, and new phase formation commenced. After exposure to 1000 °C the specimens appeared virtually amorphous or formed stuffed silica structures of nepheline- or carnegieite-type type.
The investigations of the OPG based mortars on their resistance against sulfuric acid in accordance with DIN 19573 (Appendix A) revealed very high residual strengths up to 78 % after treatment with H2SO4 (pH 1) for 70d. A mechanism of dissolution of the primary aluminosilicate reaction products of the pastes and the precipitation of a silica gel that protects the remaining aluminosilicates and decelerates further corrosion was found to be the main reason for the good performance under acidic conditions. The addition of CaO-containing feedstocks enhanced hardening, but at a certain content the resistance against sulfuric acid decreased, due to the formation of gypsum on exposure to sulfate.
In addition, the mortars exhibited excellent shrinkage behavior as well as good bond to concrete substrates with pull-off strength up to > 3 MPa. The workability of the fresh mortars provided very good manual applicability; automatic applications such as sprayed and spun mortars will require further optimization regarding rheological properties. In summary, the studied OPG are promising materials for the construction and the repair of concrete structures, such as sewers, that are affected by biogenic sulfuric acid corrosion.
The electrochemical behavior of UNS N08031 was investigated as a function of electrode potential in Green-Death solution at 40 °C. The UNS N08031 surface is in a stable passive state during cyclic potentiodynamic polarization without an initiation and/or propagation of localized corrosion. In potentiostatic polarization of UNS N08031 for 3600 s, passive current density increases with an increase in the passivation potential from 0.7 to 1.0 VSSE (silver/silver chloride reference electrode in saturated potassium chloride) Electrochemical impedance spectroscopy (EIS) and Mott-Schottky (M-S) analysis showed that a more defective n-type semiconductive passive film forms as the potential increases. X-ray photoelectron spectroscopy (XPS) revealed that passive film consists of mainly chromium and minor iron and nickel oxides. The mechanism of the defective passive film formation is discussed. The increase of the applied potential is considered to be a reason for the change in passive film stability.
Mixing and curing of geopolymers and related alkali-activated materials without storage and handling of highly alkaline solutions possesses advantages regarding safety and economic viability; one possible approach is to produce these materials from solid silica feedstocks and solid sodium aluminate, and subsequent mixing with water. We present a comparison between geopolymers and geopolymer-zeolite composites synthesized by this route from different silica feedstocks (by-product silica from chlorosilane production, microsilica, rice husk ash) and with different SiO2/Al2O3 ratios, using results from XRD, NMR, SEM, thermal analysis, mechanical and acid resistance testing. The use of rice husk ash favors formation of a fully amorphous geopolymer with high strength. Utilization of the other silica feedstocks leads to formation of geopolymer-zeolite composites, the amount and kind of zeolites depending on the feedstock and the SiO2/Al2O3 ratio. These composites show beneficial dehydration behavior, viz. no distinct dehydration step of thermal strain, with the phase assemblage after heating to 1000 °C controlled by the starting composition. Mortars produced from both, the geopolymers as well as the compo¬sites, exhibit high resistance to sulfuric acid attack, making them promising materials for the construction and the repair of industrial and sewer structures.