Combined nuclear magnetic resonance methods in quality control of lubricants in green energy production.

NMR methods were applied for lubricant analysis. Different factors influence the real aging of lubricants on diverse length scales and are captured by NMR. Chemical conversion of additives is addressed by NMR spectroscopy. High-field NMR experiments allow the identification and quantification of chemical components and are transferred to benchtop devices. Molecular dynamics and contaminations like fuel or abrasion are addressed via NMR relaxation and diffusion. Quality parameters were extracted via suitable data analysis of NMR raw data, which allow the detection of aging and indicate changes in the oil composition. At the same time, the methodology is optimized to the conditions in quality control. The feasibility is shown the example of a series of lubricants from applications in regenerative energy production, namely, wind turbine oils and biogas motor oils.

Inline NMR via a Dedicated V-Shaped Sensor.

Process monitoring and control require dedicated and reliable measures which reflect the status of the process under investigation. Although nuclear magnetic resonance is known to be a versatile analytical technique, it is only seldomly found in process monitoring. Single-sided nuclear magnetic resonance is one well known approach for being applied in process monitoring. The dedicated V-sensor is a recent approach that allows the inline investigation of materials in a pipe non-destructively and non-invasively. An open geometry of the radiofrequency unit is realized using a tailored coil, enabling the sensor to be applied for manifold mobile applications in in-line process monitoring. Stationary liquids were measured, and their properties were integrally quantified as the basis for successful process monitoring. The sensor, in its inline version, is presented along with its characteristics. An exemplary field of application is battery production in terms of anode slurries; thus, the first results on graphite slurries will demonstrate the added value of the sensor in process monitoring.

Nuclear magnetic resonance/magnetic resonance imaging on lubricating greases: Observation of bleeding and aging.

Lubricating greases were investigated by nuclear magnetic resonance/magnetic resonance imaging (NMR/MRI) to get insight into their structure and into their response to mechanical forces, which is related to bleeding and aging. The investigated greases are based on metallic soaps of fatty acids and oils, whereby LiOH is often used. These organic soaps act as thickeners and provide a network in which oils and their additives are embedded. Lubricating greases can thus be considered as a class of substances similar to oleogels or even hydrogels. Questions arise about translational mobility of guest molecules, mainly base oil, in these networks. Molecular structuring and interactions within the network of thickeners are of interest as they are related to macroscopic stability. Apart from NMR spectroscopy (1 H-, 7 Li- and 31 P-NMR), spectrally resolved relaxation and diffusion measurements are used for characterization. In addition, magic angle spinning (MAS)-NMR was combined with 1 H-MRI to investigate the impact of mechanical stress and swelling of lubricating greases.

NMR Relaxivities of Paramagnetic Lanthanide-Containing Polyoxometalates.

The current trend for ultra-high-field magnetic resonance imaging (MRI) technologies opens up new routes in clinical diagnostic imaging as well as in material imaging applications. MRI selectivity is further improved by using contrast agents (CAs), which enhance the image contrast and improve specificity by the paramagnetic relaxation enhancement (PRE) mechanism. Generally, the efficacy of a CA at a given magnetic field is measured by its longitudinal and transverse relaxivities r1 and r2, i.e., the longitudinal and transverse relaxation rates T1-1 and T2-1 normalized to CA concentration. However, even though basic NMR sensitivity and resolution become better in stronger fields, r1 of classic CA generally decreases, which often causes a reduction of the image contrast. In this regard, there is a growing interest in the development of new contrast agents that would be suitable to work at higher magnetic fields. One of the strategies to increase imaging contrast at high magnetic field is to inspect other paramagnetic ions than the commonly used Gd(III)-based CAs. For lanthanides, the magnetic moment can be higher than that of the isotropic Gd(III) ion. In addition, the symmetry of electronic ground state influences the PRE properties of a compound apart from diverse correlation times. In this work, PRE of water 1H has been investigated over a wide range of magnetic fields for aqueous solutions of the lanthanide containing polyoxometalates [DyIII(H2O)4GeW11O39]5- (Dy-W11), [ErIII(H2O)3GeW11O39]5- (Er-W11) and [{ErIII(H2O)(CH3COO)(P2W17O61)}2]16- (Er2-W34) over a wide range of frequencies from 20 MHz to 1.4 GHz. Their relaxivities r1 and r2 increase with increasing applied fields. These results indicate that the three chosen POM systems are potential candidates for contrast agents, especially at high magnetic fields.

Dedicated NMR sensor to analyze relaxation and diffusion in liquids and its application to characterize lubricants.

A dedicated nuclear magnetic resonance (NMR) sensor was designed for the analysis of liquids. The magnets are arranged in a V shape, creating a spatially dependent magnetic field in the gap. Measurements of samples with diverse diameters are possible underdefined magnetic field gradients at a given position. The magnet thus combines properties of single sided NMR with high static magnetic field gradients and classical time domain (TD) devices with lower to almost zero gradients. The sensor can easily be adapted to the requirements of the considered investigation; probes can be customized. On the example of lubricants and their aging, the added value and applicability of this sensor in quality control are highlighted in this publication. Relaxation and diffusion were measured by Carr-Purcell-Meiboom-Gill (CPMG) while varying the echo time τe and quantified via numerical modeling. Especially, relaxation shows a high sensitivity towards aging of lubricants such as particulate abrasion and changes in molecular dynamics induced, for example, by additive depletion. The applicability of this NMR sensor in quality control is demonstrated on the example of engine and transmission oils as well as of lubrication greases.

Low-field NMR for quality control on oils.

Oil is a prominent, but multifaceted material class with a wide variety of applications. Technical oils, crude oils as well as edibles are main subclasses. In this review, the question is addressed how low-field NMR can contribute in oil characterization as an analytical tool, mainly with respect to quality control. Prerequisite in the development of a quality control application, however, is a detailed understanding of the oils and of the measurement. Low-field NMR is known as a rich methodical toolbox that was and is explored and further developed to address questions about oils, their quality, and usability as raw materials, during production and formulation as well as in use.

Characterization of newly isolated oleaginous yeasts - Cryptococcus podzolicus, Trichosporon porosum and Pichia segobiensis.

The yeast strains Cryptococcus podzolicus, Trichosporon porosum and Pichia segobiensis were isolated from soil samples and identified as oleaginous yeast strains beneficial for the establishment of microbial production processes for sustainable lipid production suitable for several industrial applications. When cultured in bioreactors with glucose as the sole carbon source C. podzolicus yielded 31.8% lipid per dry biomass at 20°C, while T. porosum yielded 34.1% at 25°C and P. segobiensis 24.6% at 25°C. These amounts correspond to lipid concentrations of 17.97 g/L, 17.02 g/L and 12.7 g/L and volumetric productivities of 0.09 g/Lh, 0.1 g/Lh and 0.07 g/Lh, respectively. During the culture of C. podzolicus 30 g/l gluconic acid was detected as by-product in the culture broth and 12 g/L gluconic acid in T. porosum culture. The production of gluconic acid was eliminated for both strains when glucose was substituted by xylose as the carbon source. Using xylose lipid yields were 11.1 g/L and 13.9 g/L, corresponding to 26.8% and 33.4% lipid per dry biomass and a volumetric productivity of 0.07 g/Lh and 0.09 g/Lh, for C. podzolicus and T. porosum respectively. The fatty acid profile analysis showed that oleic acid was the main component (39.6 to 59.4%) in all three strains and could be applicable for biodiesel production. Palmitic acid (18.4 to 21.1%) and linolenic acid (7.5 to 18.7%) are valuable for cosmetic applications. P. segobiensis had a considerable amount of palmitoleic acid (16% content) and may be suitable for medical applications.