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Vorstellung der Themen der Nachwuchsgruppe "Materialcharakterisierung und -informatik für die Nachhaltigkeit im Bauwesen" von Prof. Sabine Kruschwitz (TU Berlin und BAM)
he mutual influence of F and OH groups in neighboring sites in topaz (Al2SiO4(F,OH)2) was investigated using magic angle spinning nuclear magnetic resonance (MAS NMR) and Raman spectroscopy. The splitting of 19F and 1H NMR signals, as well as the OH Raman band, provides evidence for hydrogen bond formation within the crystal structure. Depending on whether a given OH group has another OH group or fluoride as its neighbor, two different hydrogen bond constellations may form: either OH···O···HO or F···H···O. The proton accepting oxygen was determined to be part of the SiO4 tetrahedron using 29Si MAS NMR. Comparison of the MAS NMR data between an OH-bearing and an OH-free topaz sample confirms that the 19F signal at −130 ppm stems from F− ions that take part in H···F bonds with a distance of ∼ 2.4 Å, whereas the main signal at −135 ppm belongs to fluoride ions with no immediate OH group neighbors. The Raman OH sub-band at 3644 cm−1 stems from OH groups neighboring other OH groups, whereas the sub-band at 3650 cm−1 stems from OH groups with fluoride neighbors, which are affected by H···F bridging. The integrated intensities of these two sub-bands do not conform to the expected ratios based on probabilistic calculations from the total OH concentration. This can be explained by a difference in the polarizability of the OH bond between the different hydrogen bond constellations or partial order or unmixing of F and OH, or a combination of both. This has implications for the quantitative interpretation of Raman data on OH bonds in general and their potential use as a probe for structural (dis-)order. No indication of tetrahedrally coordinated Al was found with 27Al MAS NMR, suggesting that the investigated samples likely have nearly ideal Al/Si ratios, making them potentially useful as high-density electron microprobe reference materials for Al and Si, as well as for F.
In this work, we describe the synthesis, structural and photophysical characterization of four novel Pd(II) and Pt(II) complexes bearing tetradentate luminophoric ligands with high photoluminescence quantum yields (FL) and long excited state lifetimes (s) at room temperature, where the results were interpreted by means of DFT calculations. Incorporation of fluorine atoms into the tetradentate ligand favors aggregation and thereby, a shortened average distance between the metal centers, which provides accessibility to metal–metal-to-ligand charge-transfer (3MMLCT) excimers acting as red-shifted Energy traps if compared with the monomeric entities. This supramolecular approach provides an elegant way to enable room-temperature phosphorescence from Pd(II) complexes, which are otherwise quenched by a thermal population of dissociative states due to a lower ligand field splitting. Encapsulation of These complexes in 100 nm-sized aminated polystyrene nanoparticles enables concentration-controlled aggregation-enhanced dual emission. This phenomenon facilitates the tunability of the absorption and emission colors while providing a rigidified environment supporting an enhanced FL up to about 80% and extended s exceeding 100 ms. Additionally, these nanoarrays constitute rare examples for selfreferenced oxygen reporters, since the phosphorescence of the aggregates is insensitive to external influences, whereas the monomeric species drop in luminescence lifetime and intensity with increasing triplet molecular dioxygen concentrations (diffusion-controlled quenching).
In summary, we report a highly modular solid TTA-UC system comprising of a crystalline, thermally stable PCN222(Pd) MOF with CA-coated MOF channels and with a DPA annihilator embedded in a solution-like environment in the MOF channels. This solid material displays blue upconverted delayed emission with a luminescence lifetime of 373 us, a threshold value of 329 mW*cm-2 and a triplet–triplet energy transfer efficiency of 82%. This optical application adds another facet to the versatile chemistry of PCN-222 MOFs. The design concept is also applicable to other TTA-UC pairs and enables tuning of the UCL color, for example, by replacing DPA with other dyes as exemplarily shown for 2,5,8,11-tetra-tert-butyl-perylene, that yields UCL at 450 nm. Current work aims to reduce the oxygen sensitivity and to increase the retention of the trapped annihilators in organic environments, for example, by tuning the chain length of the carboxylic acid and by coating the MOF surface. In addition, the TTA-UC efficiency will be further enhanced by reducing the reabsorption of the UC emission caused by Pd(TCPP) and by optimizing the sensitizer/annihilator interface.
Explosive spalling is caused by, among others, the thermohydraulic spalling mechanism. During this process, vaporization, dehydration, moisture-transport and condensation processes interact. As a result, a drying and dehydration zone as well as a saturated zone, known as a moisture clog, are observed inside the unilaterally-heated concrete. The presented research is focused on the experimental investigation of the underlying thermohydraulic processes.
To investigate these, a test methodology based on X-ray computed tomography (CT) and nuclear magnetic resonance (NMR) was developed. Thereby, the X-ray CT scans are carried out simultaneously during the application of a defined unilateral-heating regime on a specially-constructed specimen. This miniaturized specimen, equipped with a double-layer casing, reproduces the condition within a planar, unilaterally-heated building component.
A preliminary test methodology and the first experimental results were presented at the 5th International Workshop on Concrete Spalling in Borås, Sweden (2017). The contribution for the upcoming workshop presents an improved version of this test methodology and new results for a high-performance concrete (HPC) mixture exposed to temperatures up to 500 °C. Regarding the CT measurements, a higher time-resolution of 15 min was achieved and a quantification of the moisture changes was implemented. Due to an increase in signal quality of the NMR measurements, a pore-size specific moisture distribution can now be resolved. This allows to conclude about the moisture reconfiguration between small gel pores and larger interhydrate pores. Additionally, the NMR measurement are no longer limited to first 2.5 cm below the heated surface but a one-dimensional moisture distribution can now be estimated over the whole 10 cm long specimen.
The presented results demonstrate that the combination of X-ray CT and NMR measurements enables to image and quantify the thermally-induced moisture transport and reconfiguration from small gel pores up to macro pores. This provides important insights into the thermohydraulic damage mechanism and leads to a better understanding of spalling avoidance strategies, like the addition of polypropylene fibres.
Unilateral thermal exposure of concrete building components induces moisture transport processes that have a significant influence on the spalling behaviour of dense high-strength concrete (HSC). These transport processes are based on evaporation and condensation mechanisms of liquid and gaseous water in the pores as well as the chemically bound water within the concrete. The low permeability of HSC and the formation of a saturated zone within building components (also known as a moisture clog) leads to high water-vapour pressures, which contributes to explosive spalling. The formation of these pressures has already been verified by means of pore-pressure measurement techniques. In addition, the redistribution of the moisture within concrete specimens subject to unilateral thermal exposure has been demonstrated on fractured surfaces. Investigations by means of the nuclear magnetic resonance (NMR) relaxometry technique and neutron radiography have shown one-dimensional changes in moisture distribution during thermal exposure.
However, none of these methods has been able to depict the moisture distribution in three dimensions (3D), so the link between pore size, concrete micro-structure and moisture content is missing. The research project presented in this paper aims to fill this gap by developing a new multi-level test methodology to characterise non-destructively the temporal course of spatial moisture distribution during unilateral thermal exposure. The procedure used during this programme included the collection of X-ray 3D-computed tomography (CT) measurements using a miniaturised specimen subjected to in-situ thermal exposure and the comparison of those CT results with the results of one-dimensional NMR-relaxometry before and after the heating process.
In the first step, a mobile heating device was developed, built and tested. To simulate a unilaterally-heated construction component, a cylindrical specimen made of HSC (Ø = 40 mm, L = 100 mm) was cast into an impermeable glass ceramic shell. The ceramic shell ensured a one-dimensional moisture flux and limited the thermal expansion of the concrete. An additional high-temperature wool (HTW) insulating shell ensured a one-dimensional heat flux. The heating device, which operated using infrared radiation (IR), allowed the unilateral heating of the specimens up to 300 °C using variable heating regimes.
In the second step, the mobile heating device was integrated into the CT-scanner, which enabled the collection of measurements before, during and after heating. By subtraction of successive 3D-CT images, X-ray attenuation differences could be resolved three-dimensionally in the specimen and interpreted as changes in the moisture content.
Initial results show that this test methodology can monitor the 3D changes of moisture content inside the specimen during thermal exposure. It enables the researcher to visualise areas with moisture accumulation as well as dehydrated areas inside the specimen. Comparative one-dimensional NMR-relaxometry measurements confirm the results of the CT image analysis.
Unilateral thermal exposure of concrete building components induces moisture transport processes that have a significant influence on the spalling behaviour of dense high-strength concrete (HSC). These transport processes are based on evaporation and condensation mechanisms of liquid and gaseous water in the pores as well as the chemically bound water within the concrete. The low permeability of HSC and the formation of a saturated zone within building components (also known as a moisture clog) leads to high water-vapour pressures, which contributes to explosive spalling. The formation of these pressures has already been verified by means of pore-pressure measurement techniques. In addition, the redistribution of the moisture within concrete specimens subject to unilateral thermal exposure has been demonstrated on fractured surfaces. Investigations by means of the nuclear magnetic resonance (NMR) relaxometry technique and neutron radiography have shown one-dimensional changes in moisture distribution during thermal exposure.
However, none of these methods has been able to depict the moisture distribution in three dimensions (3D), so the link between pore size, concrete micro-structure and moisture content is missing. The research project presented in this paper aims to fill this gap by developing a new multi-level test methodology to characterise non-destructively the temporal course of spatial moisture distribution during unilateral thermal exposure. The procedure used during this programme included the collection of X-ray 3D-computed tomography (CT) measurements using a miniaturised specimen subjected to in-situ thermal exposure and the comparison of those CT results with the results of one-dimensional NMR-relaxometry before and after the heating process.
In the first step, a mobile heating device was developed, built and tested. To simulate a unilaterally-heated construction component, a cylindrical specimen made of HSC (Ø = 40 mm, L = 100 mm) was cast into an impermeable glass ceramic shell. The ceramic shell ensured a one-dimensional moisture flux and limited the thermal expansion of the concrete. An additional high-temperature wool (HTW) insulating shell ensured a one-dimensional heat flux. The heating device, which operated using infrared radiation (IR), allowed the unilateral heating of the specimens up to 300 °C using variable heating regimes.
In the second step, the mobile heating device was integrated into the CT-scanner, which enabled the collection of measurements before, during and after heating. By subtraction of successive 3D-CT images, X-ray attenuation differences could be resolved three-dimensionally in the specimen and interpreted as changes in the moisture content.
Initial results show that this test methodology can monitor the 3D changes of moisture content inside the specimen during thermal exposure. It enables the researcher to visualise areas with moisture accumulation as well as dehydrated areas inside the specimen. Comparative one-dimensional NMR-relaxometry measurements confirm the results of the CT image analysis.
Two strontium-based dicarboxylate systems [Sr(oBDC-F4)(H2O)2] (1) and [{Sr(oBDC)(H2O)2)·H2O] (2) were synthesized mechanochemically via milling of Sr(OH)2·8H2O with tetrafluorophthalic acid (H2oBDC-F4) or phthalic acid (H2oBDC), respectively. The new structures were determined ab initio from the powder X-ray diffraction (PXRD) data. Both compounds 1 and 2 crystallize in the monoclinic space group P21 /c as two-dimensional coordination polymers (2D-CPs). The determined structures were validated by extended X-ray absorption (EXAFS) data. Compounds 1 and 2 show different thermal stabilities. The fluorinated CP 1 is decomposed at 300 °C while the nonfluorinated CP 2 transforms into a new phase after thermal treatment at 400 °C. The two hydrated CPs exhibit small surface areas which increase after the thermal posttreatment for 1 but remains unchanged for the dehydrated sample of 2. Dynamic vapor sorption (DVS) experiments indicate that both the dehydrated and hydrated samples of 2 depict no significant differences in their adsorption isotherms. The DVS of water indicates that the phase transition after thermal posttreatment of 2 is irreversible.
Influence of the of dealumination and porosity on the acid sites of natural zeolite clinoptilolite
(2016)
Heavy feedstock from crude and bio oil is a widely available and renewable resource for production of fuel and starting materials for other organic valuables by cracking or hydrocracking. Catalytic processing of heavy feedstock can meet the increased demand of energy up to a great extent. It requires the application of acidic catalysts like zeolites. However, the used synthetic catalysts are difficult to recover and reuse and are mostly spent.
The use of natural zeolite as spent catalysts may open new perspectives in the chemical use of heavy feed feedstock by chemical conversion. Natural zeolites are not expensive, widely available and environment friendly. Clinoptilolite is the most abundant natural zeolite. Clinoptilolite has a crystalline structure with a defined micropore system of medium size showing unique ion exchange and sorption properties. However, it is catalytically active only in the H-form. Also certain porosity is required for improvement of the accessibility of active sites.
This paper deals with the tuning of acid properties and of the mesoporosity of the clinoptilolite by variation of the Si/Al framework ratio, extra-framework aluminum and modification of the porosity by specific acid and water vapor treatment. The preparation of hierarchical pore structures containing interconnected micro-meso-macropores is an important factor influencing the catalytic performance.
The obtained materials have been characterized by XRD, TEM, FTIR, Raman, TG/DSC. The chemical composition has been determined by ICP-AES. The porosity have been investigated by nitrogen adsorption desorption measurements. The acidity has been measured by Ammonia-TPD. The extent of dealumination, stability of the clinoptilolite against acid treatment and the change in the nature of acid sites and their local structure has been studied by solid state 29Si and 27Al MAS NMR spectroscopy in detail. The catalytic activity has been investigated in the acetalization of benzaldehyde with 1,3-butanediol. The impact of the porosity, change of the Si/Al ratio as well as present Al species on catalytic properties will be discussed.