6 Materialchemie
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- Polymers of intrinsic microporosity (3)
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- Biogene Schwefelsäurekorrosion (2)
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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.
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.
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 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.
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.
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.
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.
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.
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.