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- Geopolymers (7)
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- Faserverbundwerkstoffe (2)
- Monocarboaluminate (2)
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A silica residue from waste treatment of chlorosilane production was used together with solid sodium aluminate to test its applicability for the production of one-part geopolymers. The blend was activated with water and cured at 70 °C. The degree of reaction and strength were determined after 1, 3, and 7 days. The reaction products were analyzed by XRD and SEM/EDX. Until the third day of curing the degree of reaction of the residue reached 51 % and the strength was 8.9 MPa. The reaction product was identified as geopolymer containing zeolite A. Thus, the results confirmed that the residue may be used in the production of geopolymers. However, after 3 days of curing no further progress of reaction was observed and the strength slightly decreased, which was attributed to changes in the structure of the geopolymeric gel. It was further observed that even harsh vacuum drying left some water (presumably zeolitic water and surface hydroxyl groups) in the geopolymer.
Überwachung der Fertigungsqualität von Faserverbund - Druckbehältern mittels Schallemissionsprüfung
(2011)
Ziel der Untersuchung ist die Validierung einer Prüfmethodik zur Sicherung der Fertigungsqualität von Faserverbund – Druckbehältern unter realen Fertigungsbedingungen.
Das Verfahren basiert auf Merkmalen und zulässigen Grenzwerten, die aus Schallemissionsverläufen bei der Erstdruckprüfung abgeleitet werden.
Die Methodik konnte zuvor bereits erfolgreich an Faserverbund –
Druckbehältern mit metallischem Liner getestet und patentiert werden.
Mit den aktuellen Untersuchungen wurde die Möglichkeit des Erkennens von Fertigungsfehlern in Kohlenstofffaser/Glasfaser – Hybriddruckbehältern mit polymerem Liner evaluiert.
Dazu wurden Faserverbund – Druckbehälter mittels Schallemissionsmessung bei einer hydraulischen Erstdruckprüfung überwacht, wie sie (ohne Schallemissionsprüfung) generell zur Qualitätssicherung nach der Fertigung von Faserverbund – Druckbehältern gefordert wird.
An Druckbehältern aus einer Serienproduktion wurden die Schallemissionsverläufe registriert und die mittleren Merkmalswerte sowie deren Streuung als Referenz ermittelt. Diese werden mit den Schallemissionsverläufen von Druckbehältern mit gezielt eingebrachten Fertigungsfehlern verglichen.
Bei den Fertigungsfehlern handelt es sich um Fehler, die in der Serienproduktion auftreten können und mit den Methoden der herkömmlichen Qualitätssicherung schwer oder gar nicht nachzuweisen sind.
Alle untersuchten Druckbehälter wurden im Anschluss an die Erstdruckprüfung auf verschiedene Weise bis zum Versagen (Leckage, Bersten) beansprucht. Damit war es möglich, den tatsächlichen Einfluss der Fertigungsfehler auf den Berstdruck bzw. das Ermüdungsverhalten der Behälter zu verifizieren und die Aussagefähigkeit des Schallemissionsverfahrens zu beurteilen.
Reaction products and strength development of wastepaper sludge ash and the influence of alkalis
(2014)
Wastepaper sludge ash (WSA) from a newsprint paper mill was investigated for its mineralogical composition and its reaction products and strength development after activation with water and sodium and potassium hydroxide solutions. The results showed the WSA to consist of calcite, free lime, gehlenite, tricalcium aluminate, belite, talc, quartz and probably a glassy phase. The principle reaction product was monocarboaluminate (CO3–AFm) for the water- as well as for the alkali-activated WSA. Formation of monocarboaluminate and strength gain was more rapid for the alkali-activated WSA until 1 day of curing. However, afterwards reactions proceeded much slower when alkali solutions were used, leading to an about twice as high compressive strength for water-activated WSA mortars after 28 days of curing. The observed behavior is tentatively ascribed to a less uniform microstructure of the alkali-activated WSA. Significant differences between NaOH- and the KOH-activated WSA were not observed.
Die Zementindustrie erzeugt etwa 6-7% der globalen CO2-Emissionen und steht damit als Industriezweig vor dem Hintergrund einer anvisierten Klimaneutralität vor gewaltigen Herausforderungen. Der Prozess der Klinkerherstellung wurde über die vergangenen Jahrzehnte bereits kontinuierlich optimiert. Seit 1990 ist es der deutschen Zementindustrie gelungen, die spezifischen CO2-Emissionen der Zementproduktion u. a. durch den Einsatz alternativer, nicht fossiler Brennstoffe und durch Absenkung des Klinkergehalts im Zement um 20 % zu senken. Weitere konventionelle Minderungsstrategien versprechen jedoch nur noch wenig zusätzliche Reduktion. Im Falle des Portlandklinkers besteht die Schwierigkeit darin, dass zwei Drittel der CO2-Emissionen rohstoffbedingt durch die Entsäuerung des Kalksteins (CaCO3) anfallen, die durch die beschriebenen Maßnahmen nicht weiter abgesenkt werden können. Vielmehr wird es erforderlich sein, noch zu entwickelnde oder zu optimierende Technologien anzuwenden und ggf. alle relevanten Ebenen wie Produktion, Weiterverarbeitung und Anwendung von Zement und Beton neu zu denken. Neben technologischen Ansätzen zur CO2-Abscheidung mit nachfolgender langfristiger Speicherung (Carbon Capture and Storage – CCS) oder Verwertung (Carbon Capture and Utilisation – CCU) werden auch alternative Rohstoffe für die Zementproduktion und alternative Bindemittel in Betracht zu ziehen sein.
The production and processing of ordinary Portland cement are responsible for nearly 5% of the world C02 emissions. Due to the world’s increasing requirement for building materials, this air pollution is growing up in the next decades. Alternative cement such as geopolymers can reduce these emissions effectively, Conventional geopolymer binders, produced ffom fly ash or metakaolin as aluminosilicate source and water-glass or alkali hydroxide Solutions as activator, are often used and studied. It is known that under appropriate conditions the starting materials form a three-dimensional aluminosilicate structure and create a gel-like matrix, In our case, a silica source from wastewater treatment of chlorosilane production and solid sodium aluminate as starting materials are initiated to harden by water. This procedure is known as “just add water” or “one-part” geopolymer formulation. These composites have significant advantages for use on construction site, but their Chemical structure is not extensively analyzed. In this work, a well known one-part geopolymer is investigated by 'H and 27A1 magic-angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. Furthermore, it is shown that overlapping NMR lines can resolved with echo experiments and
In paper recycling several types of waste sludges are produced, which contain organics as well as inorganic fillers of the recycled paper, e.g. kaolinite, calcite, talc, or titanium dioxide [1,2]. Part of these sludges is incinerated to recover energy and to reduce the volume of waste to be handled. The ashes generated in this process are commonly referred to as wastepaper sludge ash (WSA). The quantities of WSA produced are large and at present much of it is still landfilled or otherwise handled entailing costs.
Depending on the composition of the recycled paper and the conditions during processing and incineration, WSA can have cementitious properties. In the present investigation a CaC03-rich WSA was analyzed for reaction products and strength development after hydration with water, 2 M NaOH solution and 8 M NaOH solution. The rationale for activating the WSA with NaOH was to assess the behaviour of the WSA when alkalis are introduced to the System or when the WSA is used as addition in alkali-activated binders.
In paper recycling large amounts of waste sludge, containing organics as well as inorganic fillers of the recycled paper, are produced. A large fraction of these sludges is incinerated; the ashes generated in this process, often referred to as wastepaper sludge ash (WSA), have the potential to be used as binder material, either alone or as supplementary cementitious material. However, ashes from different paper mills differ in their Chemical and mineralogical composition, thus, the reaction products and the properties of the hardened binders may vary s i gn i fi cantley.
In the present study, a calcite-rich WSA was analyzed for reaction products and strength development. The WSA contained, besides calcite, hydraulic phases such as tricalcium aluminate (C3A) and belite (C2S), lime as well as inert phases. When activated with water, the WSA yielded a compressive strength of up to 12.3 MPa and the major hydration product was monocarboaluminate (C4A CO2 IIH2O or C4ACH11). Activation with 2M NaOH or 2M KOH solution caused a more rapid strength gain until one day of curing, but afterwards the strength development slowed down and the strength afiter 28 days was significantly lower than for the water-activated pastes. From TG analyses it is apparent that the higher strength of the alkaliactivated pastes after one day of curing was caused by a more rapid consumption of calcite and associated formation of C4ACH11. At later curing times the amount of calcite did not change substantially and consequently strength development almost ceased.
The results demonstrate the complex influence of alkaline conditions on the hydration of WSA and show that the reaction products, which determine the durability properties of the hardened pastes (and materials made from it), of the calcite-rich WSA differ from the products of other WS As, as discussed in the article.
For fully carbon fibre wrapped pressure vessels with load sharing metallic liner (Type III), it was recognized that the state of residual stress given after the autofrettage process can change even if the vessel is stored without pressure. This change is influenced by temperature and time and has a direct effect on the residual lifetime of the vessel. To study the influence of the temperature on the state of residual stress an analytical model was applied which is based on the Classical Laminate Theory (CLT). According to the model, the critical conditions leading to a decrease in lifetime were identified. To confirm the results of the model temperature cycle tests were carried out. The results of the tests are compared with the analytical model and a finite element model. To investigate the influence of time on the state of residual stress, tests on vessels were performed. The tested vessels were aged without any pressure for a longer period of time after the autofrettage process. During these tests, the strain of the vessels was monitored.
One-part geopolymers were synthesized from two different silica materials (a silica-rich residue from chlorosilane production and a commercial microsilica) and sodium aluminate at three different SiO2/Al2O3 ratios and a nominal water/solids ratio of 0.5. The degree of reaction of the silica in the cured geopolymers (i.e. the fraction of silica dissolved to form aluminosilicates and minor products) was determined using two different methods: chemical attack with HCl to dissolve the reaction products and evaluation of peak areas of 29Si MAS NMR spectra. It was found that the degree of reaction of the silica decreases with increasing the silica content of the starting mix, and that it is almost constant after 1 day of curing and almost independent from the kind of starting silica. From the results of the NMR-based method, the mean SiO2/Al2O3 ratio of the reaction products (aluminosilicates and minor products) can be estimated to be ca. 2.0, nearly independent of the starting composition of the geopolymers. The dissolution method is biased, but of sufficient precision to be useful for following changes of the degree of reaction. Major crystalline phases in the cured geopolymers are zeolite A and/or hydrosodalite. Depending on the starting composition, the relative amounts of these zeolites vary; additionally, sodalite (only for the residue from chlorosilane production with >1 wt% Cl-), faujasite, and zeolite EMT can appear in the geopolymers. The 29Si and 27Al MAS NMR results indicate mainly Si(4Al) and Al(4Si) sites, in line with the presence of zeolite A, hydrosodalite, sodalite, and geopolymeric gel of comparatively low SiO2/Al2O3 ratio.
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.
One-part alkali-activated (geopolymer) mortars based on three different silica-rich starting materials and sodium aluminate, with and without ground granulated blast furnace slag (GGBFS) addition, were tested regarding sulfuric acid resistance according to DIN 19573:2016-03 (70 days at pH = 1). Corresponding pastes were characterized by XRD, SEM, chemical analysis, 29Si MAS NMR and 1H-29Si CPMAS NMR after water storage and after acid exposure. The mortars exhibited a high resistance against sulfuric acid attack, with the best ones conforming to the requirements of DIN 19573:2016-03. The analytical results showed that this was due to precipitation of silica gel at the acid-mortar interface, which formed a mechanically stable layer that protected the subjacent mortar and thus inhibited further degradation. The addition of GGBFS decreased the acid resistance via formation of expansive calcium sulfate phases.
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.
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 aluminosilicate gel-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 aluminosilicate gel-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 composites, exhibit high resistance to sulfuric acid attack, making them promising materials for the construction and the repair of industrial and sewer structures.
One-part geopolymers, synthesized from three different silica sources and sodium aluminate, were investigated regarding their microstructure and the evolution of their compressive strength on curing at slightly elevated temperatures. The effect of thermal treatment was studied up to 1000 °C and for the investigation of the chemical durability specific samples were treated with sulfuric acid (H2SO4, pH = 1).
Depending on the silica feedstock, different degrees of reaction were observed. One of the silicas had a significantly higher reactivity. For two of the silicas, significant amounts of zeolites occurred as reaction products besides geopolymeric gel, whereas the more reactive silica source lead to the formation of a rather fully condensed geopolymeric network.
The composites indicated promising behavior on heating in so far as no distinct shrinkage step occurred in the temperature range of dehydration. Up to 400 °C the residual strength of those mixes increased. Above 800 °C the samples underwent new phase formation. After exposure to sulfuric acid (pH 1; 70 d) specimens showed a residual compressive strength of about 77 % of the reference, indicating high acid resistance.
The influence of starting materials and synthesis route on the properties and the structure of cementitious sodium aluminosilicate gels is not fully understood, partly due their amorphous nature and the fact that they often contain residual reactants, which can make the results of single-pulse NMR spectroscopy applied to these materials difficult to interpret or ambiguous. To overcome some of these limitations, 29Si{27Al} TRAPDOR NMR as well as 27Al{29Si} and 27Al{1H} REDOR NMR spectroscopy were applied to materials synthesized by the one-part alkali-activation route from three different amorphous silica starting materials, including rice husk ash. The latter led to formation of a fully amorphous sodium aluminosilicate gel (geopolymer), while the materials produced from the other silicas contained amorphous phase and crystalline zeolites. Application of the double-resonance NMR methods allowed to identify hydrous alumina gel domains in the rice husk ash-based material as well as significantly differing amounts of residual silica in the three cured materials. Four-coordinated Al existed not only in the aluminosilicate gel framework but also in a water-rich chemical environment with only a small amount of Si in proximity, likely in the alumina gel or possibly present as extra-framework Al in the aluminosilicate gel. The results demonstrate how the employment of different silica starting materials determines the phase assemblage of one-part alkali-activated materials, which in turn influences their engineering properties such as the resistance against chemically/biologically aggressive media.
Entwickelt und validiert - Probengeometrie zur Untersuchung von gewickelten Faserverbundproben
(2012)
Durch die beschriebene, auf eine Umfangsbelastung ausgelegte Probengeometrie werden
Fertigung und Einsatz von Druckbehältern nachempfunden. Dafür wurden bereits bestehende
Probenformen überarbeitet, um im Probenkörper eine unidirektionale Zugbelastung zu
erzeugen. Da die endgültigen Eigenschaften von faserverstärktem Kunststoff erst in der
Fertigung entstehen, sind gleiche Fertigungsbedingungen von Proben und Bauteilen wichtig.
Die hier vorgestellte Probe verspricht dadurch eine gute Eignung für den Einsatz bei Untersuchungen
zum Zeitstandsverhalten.