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Life-Cycle Assessment of Low-Carbon Technologies from Screening to Integrated Energy System Design - Dr Sarah Deutz - Bog - Verlag G. Mainz -

Life-Cycle Assessment of Low-Carbon Technologies from Screening to Integrated Energy System Design - Dr Sarah Deutz - Bog - Verlag G. Mainz -

Climate change mitigation requires a massive reduction of greenhouse gas (GHG) emissions and even negative emissions in the near future. To achieve GHG mitigation, low-carbon technologies are developed. However, environmental benefits are not generally proven since most technologies require significant amounts of low-carbon energy and interact in complex energy systems. Moreover, low-carbon technologies comprise a wide range of maturity and varying data availability. Assessing the full range of low-carbon technologies requires life-cycle assessment (LCA), from screening to an integrated energy system design at the concept, process, plant to system level. At the concept level, we demonstrate handling of limited data availability and apply an LCA-based short-cut method enabling a best-case ranking of CO2-based chemicals. Half of these products have the potential to provide environmental benefits already today through shortened synthetic pathways and low H2 demand. In contrast, the other products could only achieve environmental benefits when sufficient low-carbon electricity is available. Using a process from the best-case ranking, we expand the LCA model scope to the process level providing a more detailed environmental assessment for the example of CO2-based oxymethylene ethers (OME) fuels. Our well-to-wheel analysis shows a significant potential to decrease local pollutants, whereas climate impacts are only reduced if large amounts of low-carbon energy are available. Subsequently, we extend the LCA model scope to the plant level exemplary for direct air capture (DAC). We demonstrate that climate benefits strongly depend on the electricity supply and the subsequent application of CO2: permanent storage leads to negative emissions, whereas using CO2 as feedstock for fuels could reach carbon neutrality at best. Furthermore, large-scale deployment of DAC, e. g., capturing 1% of global annual CO2 emissions, will not be limited by energy and materials requirements and will increase other environmental impacts by much less than 1%. Our analyses emphasize the environmental potential of low-carbon technologies and their dependence on low-carbon energy; however, neglecting their cross-sectoral interconnectivity in the energy system. Therefore, we extend the scope of LCA to the system level by developing an energy system model with integrated LCA. The computed low-carbon transition pathways lead to many co-benefits in other environmental impact categories but also cause burden-shifting, which needs to be considered when developing climate mitigation strategies.

DKK 460.00
1

Optimization of Low-Carbon Energy Systems from Industrial to National Scale - Dr Nils Julius Baumgartner - Bog - Verlag G. Mainz - Plusbog.dk

Optimization of Low-Carbon Energy Systems from Industrial to National Scale - Dr Nils Julius Baumgartner - Bog - Verlag G. Mainz - Plusbog.dk

Climate change mitigation requires a reduction of greenhouse gas (GHG) emissions. The main emitter of GHG emissions is the energy sector, which today is based on fossil fuels. To mitigate climate change, we need to transform the energy systems to low-carbon technologies. For this purpose, new energy system designs are required along with appropriate operational strategies. In principle, these new designs and operational strategies can be identified best using mathematical optimization. However, low-carbon technologies impose challenges in solving and assessing the resulting optimization problems. Low-carbon technologies are volatile, which increase the complexity of optimal synthesis and operation. To cope with the complexity of operational optimization, we develop a time-series decomposition method. The method decomposes the complex, time-coupled operational problem into smaller subproblems, while still providing feasible, near-optimal solutions. For the increased complexity in synthesis problems, we propose a method based on time-series aggregation. The method divides the original synthesis problem into two separate problems: one aggregated relaxed problem and another aggregated restricted problem, leading to feasible, near-optimal solutions. In addition, the transformation process requires a rigorous assessment of greenhouse gas emissions and potential burden-shifting. In particular, the assessment of emissions due to electricity usage on the industrial scale is difficult, as the underlying national electricity system is not modeled. Therefore, we propose methods to compute industrial greenhouse gas emission factors for electricity. By exploiting these emission factors, industrial energy systems can significantly reduce their emissions. On the national scale, burden-shifting towards environmental impacts besides climate change needs to be prevented in the transformation. Hence, we develop a national energy system model and extend the optimization with life-cycle assessment considering 15 further environmental impacts. With the model, we compute a cost-optimal transformation pathway to a low-carbon energy system. The transformation leads to many co-benefits, but also to severe burden-shifting, which needs to be considered during the transformation process and in the development of new low-carbon technologies. Overall, the methods and models in this thesis facilitate the integration of low-carbon technologies in energy systems.

DKK 445.00
1

Lewis Acidic Alkali Metal and Aluminum Complexes - Dr Hassan Osseili - Bog - Verlag G. Mainz - Plusbog.dk

Decarbonization of Copper Production by Optimal Demand Response and Power-to-Hydrogen - Dr Fritz Thomas Carl Roben - Bog - Verlag G. Mainz -

Decarbonization of Copper Production by Optimal Demand Response and Power-to-Hydrogen - Dr Fritz Thomas Carl Roben - Bog - Verlag G. Mainz -

To avoid greenhouse gas (GHG) emissions and mitigate climate change, low-carbon technologies must be used to provide renewable energy and replace fossil fuels. However, this system transition is very material-intensive and leads to high demand for critical materials. Copper is such a material that is essential for electrical applications and many low-carbon technologies. The production of copper itself is an energyintensive process. Thus, two challenges arise that are addressed in this thesis: the flexible process operation in a fluctuating renewable energy system and the avoidance of process-based GHG emissions. The flexible operation of electricity-intensive processes can support the power grid and provide economic benefits. Demand response (DR) describes operational adjustments based on an economic incentive, such as fluctuating electricity prices. Our initial analysis shows a large DR potential of two electricity-intensive process steps in copper production. To consider the DR potential of the entire production process and to capture the dependencies of the many process steps, we formulate a detailed scheduling model of a representative copper production process. The developed mixed-integer linear program (MILP) allows minimizing the electricity costs without reducing the production volume. This process-wide scheduling enables significant DR potential, reducing annual electricity costs by up to 14.2% and shifting large parts of the electricity demand. Avoiding process-based GHG emissions is challenging because fossil fuels are hard to substitute in some processes. These processes use fossil fuels as high-temperature process heat and as chemical reducing agents. A promising alternative for these use cases is hydrogen (H2), when H2 is produced from renewable electricity using water electrolysis (Power-to-H2). The oxygen produced as a by-product offers further benefits as it can be utilized in copper production. To optimally design a power-to-H2 system, we formulate a MILP that minimizes the total annualized cost. The resulting CO2 abatement costs are 201EUR/t CO2-eq, which exceeds the current prices of EU allowances. However, a sensitivity analysis shows great potential through further development of water electrolysis. Decarbonization through Power-to-H2 offers additional DR potential. Our scheduling model of the decarbonized copper production shows that DR strongly contributes to low CO2 abatement costs. Consequently, this work identifies the potential of decarbonized copper production that provides a critical material for low-carbon technologies and supports the power grid through DR.

DKK 435.00
1

Advances in low-field NMR relaxometry - Dr Denis Jaschtschuk - Bog - Verlag G. Mainz - Plusbog.dk

Advances in low-field NMR relaxometry - Dr Denis Jaschtschuk - Bog - Verlag G. Mainz - Plusbog.dk

In the context of this work, three unilateral NMR sensors were designed, constructed and characterized. For the new sensors, the concept was chosen to vary the angle of the polarization of the magnets. This affects the size and the position of the sensitive slice. The MOUSEPAD, based on the modified design of the Profile NMR-MOUSE with 5 mm penetration depth, achieved a penetration depth of 17 mm. The Mini-MOUSEPAD is based on the Mini-MOUSE and has an increased penetration depth of 2.5 mm. The penetration depth is a crucial parameter for investigations with unilateral NMR, since the object of interest can be arbitrary shaped and the relevant areas at higher depths might be difficult to access. Therefore, these sensors might show a strategy for further miniaturization of state-of-the-art unilateral NMR sensors. The special magnet arrangement of both sensors results in a reduction of the magnetic field strenght (4.9MHz for the MOUSEPAD and 9.0 MHz for the Mini-MOUSEPAD) and much lower gradient strenght compared to prior state of the art sensors. Consequently, the weaker diffusive attenuation leads to a decreased diffusion weighting. Furthermore, in combination with the extended lateral size of the sensitive area, it leads to an increased SNR, compared to the PM5 and Mini-MOUSE. Sensors with higher sensitivity benefit from shorter measurement times and a higher information density. The third sensor is the Hexarray. It is a compact (110 x 95 x 30 mm³, 1.6 kg) unilateral sensor with two sensitive clices. It operates at 4.9 MHz at 4 mm above the sensor surface. If one coil is oerated while the other is in the waiting period and vice versa it is possible to perform measurements quasi-simultaneously without any mutual interactions. The setup can be used to reduce the measurements time. If both spots measure a similar sample, this setup can be used to increase the SNR by adding up both decays. To exploit the full potential of these sensors, further work is necessary.

DKK 445.00
1

Continuous-Amplitude Error Protection of Discrete-Time Signals - Dr Tim Schmitz - Bog - Verlag G. Mainz - Plusbog.dk

Continuous-Amplitude Error Protection of Discrete-Time Signals - Dr Tim Schmitz - Bog - Verlag G. Mainz - Plusbog.dk

Transmitting analog audio, video, or sensor data with a digital system requires sampling and quantization. While a sampled bandlimited signal can be reconstructed perfectly if the Nyquist-Shannon sampling theorem is met, quantization unavoidably adds irreversible errors. Given a certain bitrate for quantization (or source coding in general), the achievable signal quality is therefore limited. Transmission of the signal over a noisy channel causes additional errors. If some part of the bitrate is used for protecting the signal with a channel code, these additional errors can be reduced or even eliminated. However, this reduces the achievable maximum quality if the gross bitrate is fixed. Since this compromise between quantization and channel coding is often designed for the worst-case channel, the signal quality saturates early with increasing channel quality, and transmission over a better channel is far below optimum. Instead of conventional digital systems, this thesis covers a continuous-amplitude, discrete-time system. Such a system does not exhibit this saturation of the signal quality, as its performance further improves with increasing channel quality. An example of such a system is a channel coding strategy using analog modulo block codes (AMB codes) for error protection. The encoder multiplies the unquantized symbol vector with a code matrix and limits the transmission power with a modulo operation. In practice, AMB coding is implemented by digital signal processing. The digital representation of the information symbols can be very precise and no coarse quantization is required for bitrate reduction. In this thesis, AMB codes are analyzed, designed, and evaluated. The resulting code words, consisting of a lattice and a continuous component, are presented and analyzed. New decoding techniques are developed and evaluated. Additionally, a novel method to analytically estimate the quality of the decoded signal in terms of signal-to-distortion ratio (SDR) can replace computationally much more demanding simulations in many cases. This estimation strategy allows evaluating the usefulness of codes with different dimensionalities. A new, efficient design concept is developed for codes with a single input symbol, which are most promising in terms of complexity and performance. Asystem using AMBcodes outperforms traditional digital transmission systems with short block lengths for medium to high signal-to-noise ratios on the channel. Due to their typically very short block length and low encoding complexity, AMB codes are especially well suited for low-delay, low-power applications, such as hearing aids, wireless microphones, and wireless sensor networks.

DKK 445.00
1

Advances in NMR spectoscopy and imaging - Dr Alexander Gorges - Bog - Verlag G. Mainz - Plusbog.dk

Advances in NMR spectoscopy and imaging - Dr Alexander Gorges - Bog - Verlag G. Mainz - Plusbog.dk

Nuclear Magnetic Resonance (NMR) techniques have proliferated in many fields of science and technology like bio-sensing, chemical reaction monitoring and material characterization. Since the inception of NMR as an analytical tool, improving the sensitivity by increasing the field strength has been the primary development goal. However, in order to reduce cost and environmental impact, the trend to miniaturized NMR devices and its diverse application fields enjoys increasing interest. The first part of this thesis introduces novel insights into low-power rf-excitation, which is one crucial aspect for enabling further development in this direction, by employing Frank sequences. Based on experimental data, a detailed evidence of the power savings by excitation in the linear regime is given aiming at future elimination of the rf-amplifier from the NMR spectrometer so as to allow further mobility improvements. Selective excitation by colored Frank-sequence is reported, which bears promise for solvent signal suppression and motion tagging in magnetic resonance imaging (MRI). To this end, spectroscopic quality as well as image resolution with Frank excitation was significantly improved. The aim of the second part is to provide quantitative 3D moisture content patterns of natural soil samples on the microscale, which are essential for improving geological simulations on the field scale. In the course of this, the standardized imaging sequences ’zero echo time’ (ZTE) and ’ultra-short echo time’ (UTE) were employed but also Frank-sequence excitation was implemented, reflecting its first genuine application. In order to characterize water-retention behavior of the soil samples, ZTE experiments were combined with standardized geological methods like Multi-Step Outflow (MSO) and tensiometric measurements. Compared to the established way of acquiring water-retention data, the introduced method provides a fast and precise method with low effort.

DKK 445.00
1

Novel Acceleration Methods and Improved Transition State Finding Approaches for the Automatic Exploration of Reaction Networks - Dr Lukas Krep - Bog -

Novel Acceleration Methods and Improved Transition State Finding Approaches for the Automatic Exploration of Reaction Networks - Dr Lukas Krep - Bog -

Reaction models are important for many engineering tasks, such as the optimization of internal combustion engines or production lines in the chemical industry. The automated reaction space exploration method ChemTraYzer attempts to alleviate the often time-consuming reaction model development process. ChemTraYzer uses reactive Molecular Dynamics (rMD) simulations to find the underlying reactions of the reaction process. Coupling the rMD output to quantum-mechanical reoptimizations of reactant, product and transition state (TS) geometries and to transition state theory, allows ChemTraYzer to produce kinetic and thermochemical data with the low uncertainties,which are required for many reaction model applications. In this thesis, I address two major issues of the ChemTraYzer method. First, I introduce two acceleration techniques for the rMD simulations, the pressure-accelerated Dynamics (pAD) and ChemTraYzer-Temperature-Accelerated Dynamics (ChemTraYzer-TAD) methods, to extend the applicability of rMD to reaction processes that occur on longer time scales than the nanosecond. The acceleration techniques are designed to work with minimal a-priori knowledge of the reaction systems, as they are meant for the exploration of unknown reaction space. With the pAD method, I describe a methodology to choose elevated simulation pressure and temperature to speed up the occurrence of reaction events without simulating a biased reaction network. ChemTraYzer-TAD is a progression of the pAD method. ChemTraYzer-TAD allows for higher simulation temperatures than pAD and allows for high boost factors of 108 as demonstrated in our ChemTraYzer-TAD case study. Both methods are applied to case studies of low-temperature ignition reaction processes. Second, I improve the performance of the automatic TS searches, which are a bottleneck in the ChemTraYzer methodology, by introducing a recovery method for failed TS searches. Our new recovery method improves the overall TS search success rate by up to 10 percentage points to a total of 48%. Finally, I demonstrate the practical usability of ChemTraYzer for automated reaction space exploration using case studies of chlorinated dibenzofurane formation and decomposition processes.

DKK 445.00
1

Options for the Joint Evolution of Digital Terrestrial Television and Mobile Internet Access - Dr Benedikt Eschbach - Bog - Verlag G. Mainz -

Options for the Joint Evolution of Digital Terrestrial Television and Mobile Internet Access - Dr Benedikt Eschbach - Bog - Verlag G. Mainz -

Terrestrial broadcast is traditionally realized over High Tower High Power (HTHP) networks which have been preserved in the transition from the analog PAL to the first generation of the digital DVB-T technology. The drawback of this traditional network design is its spectral inefficiency. The demand for providing more TV programs with HD quality as well as the increasing spectrum consumption of mobile internet services, with video streaming being one of the driving factors, necessitate a re-optimization of the current broadcast network and a more efficient allocation of frequencies. In this thesis, three options for a future frequency-efficient evolution and coexistence of terrestrial TV and mobile internet are specified and investigated: – Transition from the current terrestrial broadcast with DVB-T to its successor DVB-T2 while retaining the HTHP network infrastructure – Switch-over from DVB-T to DVB-T2 with transition to a Low Tower Low Power (LTLP) network infrastructure – Utilization of the evolved Multimedia Broadcast/Multicast Service (eMBMS) within an existing LTLP LTE network. All three system concepts are evaluated in terms of bit error rate performance and system throughput. Additionally, coverage and total network transmit power are determined by system level simulations for different propagation models and network topologies. Although the emphasis of this thesis is on the evaluation of the performance and feasibility of the three scenarios from a technical point of view, political, regulatory, and economic considerations are addressed in short. In summary, all three options bear a huge potential for a significant reduction of the spectrum required for terrestrial broadcast. The introduction of DVB-T2 for terrestrial broadcast is a good compromise between performance, cost, and regulation. However, its full spectral potential can only be exploited in combination with LTLP network concepts. Furthermore, this thesis proves the importance of alternative terrestrial broadcasting concepts, which are highly beneficial for a further convergence of TV and mobile internet. The enhanced multimedia service eMBMS (LTE and 5G) represents an attractive solution for replacing or supplementing future terrestrial broadcast systems, especially for the distribution of personal and regional TV content.

DKK 460.00
1

Experiments and Validated Models for Adsorption Thermal Energy Storage in Industrial and Residential Applications - Dr Heike Schreiber - Bog - Verlag

Experiments and Validated Models for Adsorption Thermal Energy Storage in Industrial and Residential Applications - Dr Heike Schreiber - Bog - Verlag

Thermal energy storage (TES) helps to reduce energy consumption and peak demands by balancing heat supply and demand on all time scales from short-term to seasonal. Thus, TES is an important technology to improve flexibility and efficiency of energy systems. In particular, adsorption TES systems, which exploit the enthalpy of adsorption, provide high energy storage density and high efficiency. The present thesis therefore analyzes an adsorption TES unit for residential and industrial applications. Industrial energy supply can be made more efficient by integrating waste heat into the process heat supply and by using energy-efficient technologies. Adsorption TES contributes to both approaches: waste heat can be integrated via the heat pump effect and TES allows for energy-efficient cogeneration heat supply for batch processes. We evaluate the energy efficiency of the heat supply for an industrial batch process by adsorption TES and cogeneration. To evaluate the performance, a dynamic model of an adsorption TES unit is developed. Measurements from earlier experimental investigations of an adsorption TES unit are used to calibrate the storage model. As benchmark, a peak boiler and TES based on a phase-change material are considered. Our comparison demonstrates the significance of the process conditions for the choice of the appropriate technology. The study shows that adsorption TES offers significant potential to increase the energy efficiency: primary energy consumption can be reduced by up to 25%. The key is the availability of low-grade heat at times of discharging and of a low-grade heat demand when charging the storage unit. The study reveals that a comprehensive evaluation of the storage performance requires dynamic models that precisely describe the storage performance and the heat losses in particular. The present thesis provides the basis with a new experimental setup to precisely characterize the adsorption TES unit. In an experimental analysis of the TES performance, we quantify the heat losses, the energy recovery ratio (69–91%) and the energy storage density (20.4 kWh/m3) of the adsorption TES unit for varying charging temperatures and storage times ranging from continuous operation to seasonal storage. The extensive experimental study provides the basis to improve our model of the adsorption TES unit. The model is calibrated to heat-loss measurements and a storagecycle measurement. We quantify the simulation accuracy and validate the model with measurements at various process conditions. The model achieves a higher prediction accuracy than other models from literature. The thesis thus provides a basis for future investigations of energy systems to exploit the advantages of adsorption TES.

DKK 445.00
1

Studies of Tangible Cultural Heritage with Portable Stray-Field NMR - Dr Christian Rehorn - Bog - Verlag G. Mainz - Plusbog.dk

Studies of Tangible Cultural Heritage with Portable Stray-Field NMR - Dr Christian Rehorn - Bog - Verlag G. Mainz - Plusbog.dk

Sensors for stray-field nuclear magnetic resonance (NMR) have been employed to measure tangible cultural heritage since they were first conceived. Although NMR is a method with inherently low sensitivity and requires larger amounts of time than many other techniques, it is non-destructive and grants access to spin densities and relaxation times, physical quantities which are exclusive to the method. This thesis describes theory, instrumentation, and applications of unilateral NMR in the field of cultural heritage. The detection zone of an NMR-MOUSE, a sensor developed and maintained by past and present members of the group of Professor Blümich, is mapped through back-projection for the first time. Traditionally, the signal arising from the detection volume was averaged over multiple scans until the signal response was satisfactory. In this work, an algorithm is proposed to improve the signal-to-noise ratio in magnetization decays as a method of post processing an output, which contains the individual data from smaller sub-experiments. One of the most prominent fields of application for unilateral NMR is the investigation of porosity in stone and soil. In a study of ancient mortars in Herculaneum, a city buried by the ashes of Mount Vesuvius during the famous eruption of 79 AD, the profiles of over 60 sites, fragments and mock-ups were compared for the first time with methods known from statistics and pattern recognition. The effects of high temperatures up to 900 °C on low and high-density sandstone were determined in terms of their transverse relaxation times. Mock-ups were cross referenced with actual walls and fragments to assess the damage of the western wall of the burnt down Mackintosh Library in Glasgow. Studies of paint show how stray-field sensors can help evaluating solvent activity and their potential as cleaning agents. Relaxation times assess embrittlement and transient softening caused by such treatments. Furthermore, the potential to detect or even discriminate natural and artificial aging of binder polymers is explored. The impressive sound and quality of historic instruments by Stradivari and his contemporaries is still unsurpassed in the opinion of many musicians, but the reason for this remains controversial. When tested with unilateral NMR, violins and violas from the golden age of luthiers revealed a homogeneous wood density throughout their maple back plate. Shorter relaxation times at the wood surfaces may be traces of previous treatments. Even though unilateral NMR equipment was claimed to be portable for many years, it had relied on grid power and shielding from weather. This work presents the efforts of measuring biofilms in Yellowstone National Park, relying on battery power to perform the non-destructive tests. An NMR-MOUSE was constructed and waterproofed to detect biofilms under water and in-situ.

DKK 445.00
1

Construction of Rate-Compatible Codes from Punctured Polar Codes - Dr Christopher Matthisa Schnelling - Bog - Verlag G. Mainz - Plusbog.dk

Construction of Rate-Compatible Codes from Punctured Polar Codes - Dr Christopher Matthisa Schnelling - Bog - Verlag G. Mainz - Plusbog.dk

Transmitting information enables technical applications modern societies are built on. This thesis focuses on channel coding, a fundamental building block of communications systems that transmit information using noisy channels. In his seminal work presented in 1948, Shannon laid ground for the mathematical theory of information and its transmission. Formalizing the notion of a noisy channel as a statistical model, Shannon establishes the maximum rate at which information may be transmitted. This upper bound, referred to as the channel’s capacity, is strict. At rates below the capacity of a given channel, information may be transmitted and recovered at the receiver, while there is no hope for doing so without a positive error probability at rates exceeding that capacity. To protect against transmission errors, channel codes add redundancy to the information, which supports a channel decoder located at the receiver in recovering the information. The field of channel coding is concerned with designing said redundancy to transmit at rates close to capacity. Shannon shows that this is possible using random codes, and a code length approaching infinity. However, neither random codes nor codes of infinite length are a viable way to build concrete systems. As a result, his work sparked a vast body of research concerned with building practical channel codes. Prominent early milestones are given by Hamming codes, Golay codes, as well as Reed-Muller (RM) codes. Early coding theory was dominated by algebraic approaches that exploit the structure of finite fields to devise efficient encoding and decoding algorithms for linear block codes on harddecision channels, with Bose-Chaudhuri-Hocquenghem (BCH) codes and Reed-Solomon (RS) codes marking major breakthroughs. Advances in computer technology enabled iterative decoders allowing turbo codes to approach the Shannon limit with moderate decoding complexity in the last decade of the 20th century, and lead to the rediscovery of low-density parity-check (LDPC) codes proposed by Gallager in 1963. Under iterative decoding algorithms operating on graphical representations of the parity-check matrix, the latter are shown to approach the Shannon limit on binary-input channels subject to additive white Gaussian noise. These developments solve the channel coding problem from a practical point of view. However, in 2008, Arıkan presents polar codes (PCs), the first channel coding scheme provably achieving the Shannon capacity of output-symmetric binary-input discrete memoryless channels (BDMCs) with low-complexity encoding and decoding methods. Describing the phenomenon of polarization, Arıkan shows how to create disparate mutual information terms by combining independent pairs of random variables. This results in a recursive construction that amplifies this disparity, ultimately leading to polarization. His sequential decoding algorithm exploits this phenomenon, and allows for the construction of channel codes that provably feature vanishing error probability as the code length approaches infinity. Consequently, this reignited research in coding and inspired many works that translate the polarization phenomenon to classical information-theoretic problems, but also lead to a continuously growing number of publications focusing on practical aspects of polar coding.

DKK 445.00
1

Advances in biomedical NMR with spatial resolution - Dr Jennifer Flohr - Bog - Verlag G. Mainz - Plusbog.dk

Advances in biomedical NMR with spatial resolution - Dr Jennifer Flohr - Bog - Verlag G. Mainz - Plusbog.dk

In modern medicine, magnetic resonance imaging (MRI) is an essential diagnostic tool, which enables physicians to detect a great variety of diseases and physical injuries. The scope of possibilities encompasses neuro-, cardiovascular-, musculoskeletal-, hepatobiliary- and gastrointestinal imaging as well a magnetic resonance angiography. Besides commercially available MRI scanners, low magnetic field devices gain more and more attention because they are more compact, mostly portable, easier to handle due to the lack of cryogenic coolants, and usually come with a large cost saving. In this thesis, high magnetic field devices and unilateral NMR sensors are deployed to explore different biomedical topics. Imaging techniques are used to study the flow inside aneurysms—enlargements of blood vessels in the human body, whose rupture can lead to severe health issues. In an experimental flow set-up, different fluids and flow velocities are tested inside silicon aneurysm models with and without stents. These narrow tubes, which commonly consist of a metallic network, are inserted into a vessel to cut the aneurysm from the blood stream. TheNMR-MOUSER (MObileUniversal Surface Explorer), a sensor design first conceived in the mid 90s by Blümich and Blümler, and its derivative — the Fourier NMR-MOUSE — are utilized to study human and porcine skin. Outer skin layers are investigated in terms of diffusion and relaxation time profiling in laboratory and clinical studies. They assess the structural composition and susceptibility to different substances, and identify carcinogenic processes and the effect of aging and renal insufficiency.

DKK 445.00
1

HD Telephony by Artificial Bandwidth Extension - Dr Thomas Matthias Schlien - Bog - Verlag G. Mainz - Plusbog.dk

HD Telephony by Artificial Bandwidth Extension - Dr Thomas Matthias Schlien - Bog - Verlag G. Mainz - Plusbog.dk

The audio bandwidth of digital landline and mobile telephone networks is still mostly restricted to 200 Hz to 3.4 kHz. This is due to compatibility requirements during the transition phase from analogue to digital transmission technology. The resulting characteristic "telephone speech" is widely accepted, but the intelligibility of syllables is only 91%. Meanwhile, improved coding standards for so-called “HD voice” or “Wideband Speech” have been developed which are gradually being introduced into the networks. They support an audio frequency bandwidth of 50 Hz to 7.0 kHz with significantly increased audio quality and speech intelligibility. For a very long time however, new HD-telephones and old narrowband telephones have to co-exist. If an HD-terminal is connected over a narrowband link to an old telephone, the improved coding scheme cannot be used. In this thesis, signal processing concepts are developed for improving audio quality and intelligibility of narrowband speech by artificial bandwidth extension (ABWE). These algorithms can be applied in the HD terminals or in the network, to transform narrowband speech to HD voice. Based on the source-filter model of speech production and a priori knowledge of the characteristics of speech signals, the missing frequency components between 3.4 kHz and 7 kHz are reconstructed. In comparison to the state-of-the-art ABWE approaches, the main contributions are: • new concepts of estimating the wideband spectral envelope, e.g., in terms of the model filter by interpolation in the acoustic tube domain • algorithms for spectral extension of the excitation signal • new insights concerning the relative importance of the excitation, the temporal envelope and the spectral envelope • remarkable improvements of the audio quality • significant low computational complexity • efficient and effective training and estimation algorithms The improvements are verified by objective evaluation and subjective listening tests.

DKK 445.00
1

Active Noise and Occlusion Effect Cancellation in Headphones and Hearing Aids - Dr Stefan Wilhelm Liebich - Bog - Verlag G. Mainz - Plusbog.dk

Active Noise and Occlusion Effect Cancellation in Headphones and Hearing Aids - Dr Stefan Wilhelm Liebich - Bog - Verlag G. Mainz - Plusbog.dk

The perception of one’s own voice is distorted when telephoning with headsets, or wearing hearing aids. The reason for this is the so-called occlusion effect, which occurs when ear canals are completely or partially closed by the headset or hearing aid. The occlusion causes amplification at low frequencies, and attenuation at high frequencies of one’s own voice. The unnatural perception of one’s own voice and of noise caused by chewing and swallowing are among the most common complaints of users. Furthermore, environmental noise might impair perception. In this thesis, both the unnatural perception of one’s own voice and the disturbance by environmental noise are tackled by a novel signal processing approach. The proposed solution solves the problem of the occlusion effect by actively emitting a compensation signal through the integrated loudspeaker. The approach is called Occlusion Effect Cancellation (OEC) and significantly improves the perception of one’s own voice and of the acoustic environment. This novel approach combines methods of active noise cancellation (ANC, Noise Cancelling Headphone) with a personalized design. The bilateral headset contains two additional microphones per side, one inner and one outer, to acquire signals for the calculation of the compensation signals. A correctly balanced processing of the two microphone signals results in a "digital ear opening" and a much more natural perception of both one’s own voice and of the environment. The extent of the digital ear opening is controllable. The system can also be operated as a noise cancelling headphone by changing the parameters to a conventional design to create an acoustic isolation from the environment. This thesis proposes a novel robust approach based on digital filtering to solve the described problems. A combination of feedback and feedforward filter design allows for either approaching personal silence or a natural perception of one’s own voice and the acoustic environment.

DKK 462.00
1

Designing Pathways for Net-Zero Greenhouse Gas Emission Plastics with Life Cycle Optimization - Dr Raoul Meys - Bog - Verlag G. Mainz - Plusbog.dk

Designing Pathways for Net-Zero Greenhouse Gas Emission Plastics with Life Cycle Optimization - Dr Raoul Meys - Bog - Verlag G. Mainz - Plusbog.dk

Plastics are on the rise to conquer every area of modern human life but lead to increased pollution of nature, enormous oil consumption, and large-scale greenhouse gas emissions. Thus, to avoid climate change above 1.5?C, net-zero greenhouse gas emission plastics are needed by the second half of this century. To reduce the greenhouse gas emissions associated with plastics, three circular technologies can be used: (1) chemical or mechanical recycling, (2) carbon capture and utilization, and (3) biomass utilization. However, current environmental assessments of these circular technologies focus solely on individual or partly combined circular technologies, are limited to regional scopes, and often apply inconsistent methodologies. Thus, it is currently unclear if net-zero emission plastics can actually be achieved with the current set of circular technologies. Furthermore, shifting from the linear to a circular economy is regarded as energy-intensive and costly, hindering strong policy implementation from fostering the transition to a circular economy. To assess if net-zero emission plastics can actually be achieved, this thesis builds and uses the first global, industry-wide and systematic bottom-up model for plastics production and waste treatment, representing the global life cycle greenhouse gas emissions of 90% of global plastic production. Using that model reveals that net-zero emission plastics can be achieved by combining biomass and CO2 utilization with an effective recycling rate of 70% while saving up to to 53% of energy and 288 billion USD compared to a fossil-based benchmark applying large-scale carbon capture and storage. Achieving the full potential of energy and cost savings while achieving netzero emissions requires the supply of biomass and CO2 at low cost, while cost of oil supply must be increased. To incentivize this shift, investment barriers for all available circular technologies have to be lowered by implementing consistent emission pricing schemes, using deposit systems for plastics to increase recyclability and stopping to subsidize fossil resources. Thus, this thesis shows that the greenhouse gas emission problem of plastics can be solved with technologies and solutions already available today.

DKK 415.00
1

Speech Signal Enhancement by Information Combining - Dr Florian Kurt Wolfgang Paul Heese - Bog - Verlag G. Mainz - Plusbog.dk

Speech Signal Enhancement by Information Combining - Dr Florian Kurt Wolfgang Paul Heese - Bog - Verlag G. Mainz - Plusbog.dk

Mobile phones as well as tablets are omnipresent and belong to everyday life. Today audiovisual communication takes place at different locations and in a large variety of acoustic environments. In consequence, the intelligibility as well as the quality of speech may significantly be degraded by ambient background noise. In order to improve speech intelligibility and to ensure a convenient communication with high audio quality, speech enhancement techniques are required. In this thesis all critical components contributing to the enhancement of the up-link signal are addressed: • signal capturing at the acoustic front-end with a new near field beamformer • new codebook based speech and noise estimation procedure generating and exploiting reliability information, and • actual noise reduction exploiting spectral dependencies of human speech. For the acoustic front-end of the digital processing chain a novel concept for the filter optimization of a near field beamformer is introduced. The optimization scheme allows to closely approximate a predefined reception characteristic which can be freely chosen according to the application. The output of the beamformer provides a pre-enhanced signal with improved SNR for subsequent single-microphone based speech enhancement. Single-microphone noise reduction usually relies on statistical properties of speech and noise. In general, the noise is assumed to be stationary or only slightly time-varying, which is in practice often not fulfilled. Due to imprecise noise estimation, single-microphone systems are prone to unpleasant artifacts that are called musical tones. In this context different Information Combining methods, merging various estimates, are presented which address specifically the problem of non-stationary noise signals, leading to a significant improved estimation accuracy. On the one hand, the proposed Information Combining is used with respect to spectral dependencies of human speech. On the other hand, it merges the best of several speech and noise estimates depending on their reliability. The necessary estimates are provided by a new statistical noise estimator as well as a codebook driven speech and noise estimation algorithm. The achieved estimation quality opens up the possibility to close the gap between the conflicting goals of high noise attenuation, low speech distortion, and the prevention of undesired musical tone artifacts. Finally, the practical aspects of the proposed enhancement systems are considered and discussed with two implemented real-time demonstrators.

DKK 445.00
1

Quantized Compressive Sampling for Structured Signal Estimation - Dr Niklas Koep - Bog - Verlag G. Mainz - Plusbog.dk

Quantized Compressive Sampling for Structured Signal Estimation - Dr Niklas Koep - Bog - Verlag G. Mainz - Plusbog.dk

This thesis investigates different approaches to enable the use of compressed sensing (CS)-based acquisition devices in resource-constrained environments relying on cheap, energy-efficient sensors. We consider the acquisition of structured low-complexity signals from excessively quantized 1-bit observations, as well as partial compressive measurements collected by one or multiple sensors. In both scenarios, the central goal is to alleviate the complexity of sensing devices in order to enable signal acquisition by simple, inexpensive sensors. In the first part of the thesis, we address the reconstruction of signals with a sparse Fourier transform from 1-bit time domain measurements. We propose a modification of the binary iterative hard thresholding algorithm, which accounts for the conjugate symmetric structure of the underlying signal space. In this context, a modification of the hard thresholding operator is developed, whose use extends to various other (quantized) CS recovery algorithms. In addition to undersampled measurements, we also consider oversampled signal representations, in which case the measurement operator is deterministic rather than constructed randomly. Numerical experiments verify the correct behavior of the proposed methods. The remainder of the thesis focuses on the reconstruction of group-sparse signals, a signal class in which nonzero components are assumed to appear in nonoverlapping coefficient groups. We first focus on 1-bit quantized Gaussian observations and derive theoretical guarantees for several reconstruction schemes to recover target vectors with a desired level of accuracy. We also address recovery based on dithered quantized observations to resolve the scale ambiguity inherent in the 1-bit CS model to allow for the recovery of both direction and magnitude of group-sparse vectors. In the last part, the acquisition of group-sparse vectors by a collection of independent sensors, which each observe a different portion of a target vector, is considered. Generalizing earlier results for the canonical sparsity model, a bound on the number of measurements required to allow for stable and robust signal recovery is established. The proof relies on a powerful concentration bound on the suprema of chaos processes. In order to establish our main result, we develop an extension of Maurey’s empirical method to bound the covering number of sets which can be represented as convex combinations of elements in compact convex sets.

DKK 445.00
1

Reliable and Robust Optimal Design of Sustainable Energy Systems - Dr Dinah Elena Hollermann - Bog - Verlag G. Mainz - Plusbog.dk

Reliable and Robust Optimal Design of Sustainable Energy Systems - Dr Dinah Elena Hollermann - Bog - Verlag G. Mainz - Plusbog.dk

The synthesis of energy systems is a complex task, since a plethora of conditions needs to be regarded during decision making. Thus, mathematical optimization is an excellent tool to accomplish this task and to identify an optimal system design. However, energy system synthesis is intrinsically uncertain, since the availability of components is inherently uncertain as well as the input parameters, such as energy demands. As a result, neglecting uncertainties might lead to a lack of energy supply. An insufficient energy supply possibly causes both high unexpected costs and environmental damage. Thus, uncertainties need to be regarded during optimization of energy systems. At the same time, sustainability is a further major aspect in the synthesis of energy systems. To regard sustainability performance, multiple decision criteria, such as economic, environmental, and social criteria, need to be taken into account. For this purpose, employing multi-objective optimization is perfectly suitable. However, multi-objective optimization leaves the decision maker in general with more than one solution to choose from which is often very challenging. Therefore, in this thesis, a framework to select the best reliable and robust sustainable design of an energy system is proposed – the be-rebust framework. The framework takes into account both, uncertainty of energy supply as well as uncertainty of input parameters for optimization. Thus, the designed system is reliable and robust guaranteeing security of energy supply. Sustainability is regarded by employing multi-objective optimization. For decision support, the framework automatically selects one single design. The selected design allows for highly flexible operation regarding the considered objective criteria. The proposed be-rebust framework is applied to a real-world case study. In the case study, the design of a distributed energy supply system is optimized. For this purpose, total annualized costs and the global warming impact are minimized. The results show that reliability as well as robustness can be achieved with only low additional costs. Employing the framework enables to select a sustainable design with higher operational flexibility than provided by designs identified by sole application of multi-objective optimization. The results verify the excellent performance of the proposed framework to select the best sustainable energy system design which is reliable and robust.

DKK 445.00
1

Application of Manganese Pincer Complexes for Hydrogenation and Dehydrogenation Reactions - Dr Viktoriia Zubar - Bog - Verlag G. Mainz - Plusbog.dk

Application of Manganese Pincer Complexes for Hydrogenation and Dehydrogenation Reactions - Dr Viktoriia Zubar - Bog - Verlag G. Mainz - Plusbog.dk

On the way towards sustainable and green chemistry, scientists found a key technology which allows chemical transformations to proceed with minimum waste generation and energy consumption. The key is transition metal catalysis which is also attractive from an economical point of view. At the end of 19th century, Alfred Werner defined basics of coordination chemistry which were significant for the development of transition metal catalysis. In the 1930s, the Oxo Process, in which olefins react with syngas to produce linear and branched aldehydes, was developed by Otto Roelen. The reaction is still widely used and allows to produce millions metric tons of oxo chemicals. A following milestone in transition metal catalysis occurred in the 1950s when the Wacker Process was developed. The reaction allows to oxidize olefins to aldehydes and ketones with the use of PdCl2 as catalyst. Many other reactions were developed involving transition metal catalysis, including important processes such as C-C bond formations, site selective C-H bond activation, arylation of amines and alcohols and others which have been also applied in industrial processes to obtain bulk chemicals, fine chemicals and polymers. Another indicator highlighting the importance of homogeneous transition metal catalysis is the acknowledgement by the Noble Prize committee. Thus, in 2001, the Nobel Prize in chemistry was awarded jointly to William S. Knowles, Ryoji Noyori and K. Barry Sharpless for their work on transition metal catalysed asymmetric hydrogenation and oxidation reactions. Later in 2005, Yves 0Chauvin, Robert H. Grubbs and Richard R. Schrock were selected for the Noble Prize in chemistry for their work on the development of the metathesis reaction in organic synthesis. And finally, recent Noble Prize in chemistry in 2010 was awarded to Richard F. Heck, Ei-ichi Negishi and Akira Suzuki for palladium-catalysed cross coupling reactions in organic synthesis. Until recently, reports featuring homogeneous transition metal catalysis were focused on using rare and expensive metals. The application of noble metals raises major concern, as they are toxic and consequently they produce toxic waste. And to their low availability (listed as critical raw materials for European Union), noble metals require difficult extraction from the Earth’s crust.

DKK 445.00
1

Immobilization of Ruthenium-Triphos Catalysts and their Application for the Hydrogenation of Polar Bonds in Batch and Continuous-Flow Systems - Dr

Immobilization of Ruthenium-Triphos Catalysts and their Application for the Hydrogenation of Polar Bonds in Batch and Continuous-Flow Systems - Dr

The present thesis deals with the development of immobilized Ruthenium-Triphos catalysts for the selective hydrogenation of esters, amides and CO2 as potential substrates in the context of the valorization of renewable carbon resources. The highly active molecular catalyst [Ru(Triphos)TMM] (C-1a), already investigated in various catalytic approaches and mechanistic studies, was defined as target structure for immobilization. In a detailed preparative study, two synthetic pathways towards [(Ru(Ether-Triphos)TMM] (C-2a) and [(Ru(Carbamate-Triphos)TMM] (C-3a) were developed, using a triethoxysilyl-functionality as anchoring-group in the catalysts backbone, enabling the covalent immobilization on oxidic supports (section 3.1). Subsequently, the complex [(Ru(Ether-Triphos)TMM] (C-2a) was tethered on amorphous SiO2,500, leading to the heterogenized catalyst [(Ru(Ether-Triphos)TMM]@SiO2,500 (C-2b, section 3.1). The immobilized catalyst was successfully tested in ester-, amide- and CO2 hydrogenation reactions in single-batch and continuous-flow experiments. In lactam hydrogenation reactions the immobilized catalyst showed superior long-term stability and activity in comparison to its homogeneous counterpart. Since the homogeneous complex quickly forms an inactive hydridebridged dimer under the employed reaction conditions, the active-site isolation of the tethered complexes on the surface prevents self-deactivation, thus maintaining its activity in several recycling steps. For long-term continuous-flow hydrogenation tests with C-2b, DL-lactide was evaluated as a suitable benchmark-substrate in an extensive ester screening. Here, different catalyst pre-treatments were tested to maximize catalyst activity. High TON ( 4700) over multiple days in flow were reached and the changes that the catalyst material underwent were characterized (section 3.3). After the catalytic evaluation of C-2b the observed Ru leaching was determined to be the major target for further catalyst optimization. Therefore, various modifications in catalyst preparation were performed, including changes in the synthesis order and reaction conditions, additive utilization as well as the incorporation of the complex C-2a into the framework mesostructured SBA-15 towards [(Ru(Ether-Triphos)TMM]@SBA-15 (C-2k, section 3.4). In a final investigation, selected catalysts were evaluated in the direct synthesis of dimethoxy methane (DMM) from CO2, H2 and MeOH. Catalyst C-2k was highly active and superior in terms of low Ru leaching-rates and reached unpreceded activity during recycling experiments (TON 1900 of DMM, section 3.5).

DKK 460.00
1

Ion Transport in HfO2 - Dr Michael Patrick Muller - Bog - Verlag G. Mainz - Plusbog.dk

Ion Transport in HfO2 - Dr Michael Patrick Muller - Bog - Verlag G. Mainz - Plusbog.dk

In this thesis the diffusion of anions and cations in HfO2 was investigated in detail. Furthermore, the conductivity of HfO2 was probed and approaches to interpret the results were presented. The diffusion of oxygen in dense ceramics of monoclinic HfO2 (m-HfO2) was studied by means of (18O/16O) isotope exchange annealing and Secondary Ion Mass Spectrometry (SIMS). All measured isotope profiles showed complicated behaviour in exhibiting two features: the first feature, closer to the surface, was attributed mainly to slow oxygen diffusion in an impurity silicate phase; the second feature, deeper in the sample, was attributed to oxygen diffusion in bulk m-HfO2. The activation enthalpy of oxygen tracer diffusion in bulk m-HfO2 was found to be ΔHD∗ ≈ 0.5 eV. The diffusion of cations in m-HfO2 was studied with samples prepared by cooperation partners, utilising a low-temperature preparation method, atomic layer deposition, in order to produce non-equilibrium samples. These were then used in diffusion annealing experiments and investigated with SIMS. The measured isotope profiles displayed two features, attributed to bulk diffusion and grain-boundary diffusion. A numerical analysis produced a bulk diffusion activation enthalpy of ΔHb ≈ 2.1 eV and a grain-boundary diffusion activation enthalpy of ΔHgb ≈ 2.1 eV. These values are small compared to other AO2 systems and the difference is attributed to the structural perturbations in the monoclinic system. A computational investigation of cation diffusion in m-HfO2 using Density-Functional-Theory (DFT) yielded migration enthalpies for individual cation jumps. Two jumps were found with values comparable to the experiments (≈ 2 eV), allowing long-range diffusion through the bulk. Molecular dynamics simulations in c-HfO2 with an applied field were able to reproduce the activation enthalpy of bulk diffusion determined experimentally and with DFT. However, molecular static simulations instead produce results much closer to those of other AO2 systems. A cooperative migration mechanism of oxygen and hafnium vacancies is proposed. The conductivity of m-HfO2 was studied in dependence of the oxygen partial pressure by means of high temperature equilibrium conductance measurements. In reducing conditions the total conductivity was found to increase with oxygen partial pressure. Numerical defect-chemical calculations showed that singly positively charged oxygen vacancies are likely responsible for this behaviour. In the intermediate oxygen partial pressure regime ionic conductivity dominated. In oxidising conditions the total conductivity increased with oxygen partial pressure due to electron holes.

DKK 445.00
1

A Design Approach for Adsorption Energy Systems Integrating Dynamic Modeling with Small-Scale Experiments - Dr Stefan Wilhelm Graf - Bog - Verlag G.

A Design Approach for Adsorption Energy Systems Integrating Dynamic Modeling with Small-Scale Experiments - Dr Stefan Wilhelm Graf - Bog - Verlag G.

Adsorption energy systems can be driven by thermal energy from waste heat or the sun and thereby allow reducing fossil energy consumption and thus reduce global greenhouse gas emissions. Adsorption heat pumps and chillers can provide heating or cooling, adsorption thermal energy storage allows storing thermal energy. However, adsorption energy systems suffer from high investment costs due to low performance. Performance of adsorption energy systems strongly depends on the equilibrium properties of the working pair as well as heat and mass transfer mechanisms of the adsorption material in the adsorption energy system (adsorbent configuration). Evaluating new working pairs and adsorbent configurations is rather challenging: While the working pair''s equilibrium properties can be determined with standardized measurement equipment, heat and mass transfer mechanisms cannot easily be determined, since they strongly depend on the full-scale adsorption energy system. Construction and operation of full-scale experiments requires high effort. Besides, often only small amounts of an adsorbent configuration are available, which are insufficient for full-scale experiments. To resolve these drawbacks, this thesis provides and validates a comprehensive method to determine the performance of working pairs and adsorbent configurations in adsorption energy systems from simple small-scale experiments. As a representative class of adsorption energy systems, adsorption chillers are investigated in this thesis. A small-scale Large-Temperature-Jump experiment is combined with dynamic modeling of the transient heat and mass transfer processes. Additionally, the experiment is extended by an infrared camera. The additional temperature information allows to distinguish and to determine the time-resolved effective heat transfer coefficient and diffusion coefficient in the heat and mass transfer model. The heat transfer and diffusion coefficients are inserted into a full-scale adsorption chiller model to predict the performance. Exemplarily, a commercial available silica gel and the adsorbent class of metal-organic frameworks (MOFs) are evaluated for an adsorption chiller application. The method is validated with experimental data of a full-scale prototype adsorption chiller and shows high accuracy. Furthermore, the method allows optimizing the adsorption chiller for a given working pair or adsorbent configuration and allows identifying bottlenecks and potential for improvement of the working pairs. In summary, this thesis bridges the gap between small-scale experiments and modeling of full-scale adsorption energy systems. The method allows for a comprehensive and reliable evaluation of working pairs and adsorbent configurations for adsorption energy systems.

DKK 460.00
1

Novel Concepts for Iron- and Manganese-catalyzed Homogenous Redox Transformations - Dr Aleksandra Brzozowska - Bog - Verlag G. Mainz - Plusbog.dk

Novel Concepts for Iron- and Manganese-catalyzed Homogenous Redox Transformations - Dr Aleksandra Brzozowska - Bog - Verlag G. Mainz - Plusbog.dk

Transition metal catalysis plays a crucial role in the development of new chemical transformations, which can be broadly applied in organic synthesis, medicinal chemistry, synthesis of biologically relevant molecules, pharmaceuticals and other related fields. In recent years, the need for application of sustainable methods is significantly growing due to the necessity of waste-free transformations. Plenty of industrially run processes still apply classical procedures, which often lead to production of tons of waste as a consequence of multistep synthesis. Thus, development of novel catalytic systems which would afford complex molecular structures via straightforward processes is still desired. Hence, metal-catalyzed transformations play a crucial role in the development of new synthetic strategies, as they can easily lead to the reduction of synthetic steps and, ipso facto, reduction of waste leading to atom-economic transformations. Application of transition metals particularly in homogenous catalysis was initiated by industrial processes such as carbonylation of alkenes and alkynes by metal carbonyls, production of polyethylene and polypropylene by the Ziegler-Natta catalysts or conversion of ethylene into acetaldehyde in the Wacker’s process. This breakthrough inspired investigation of other synthetic reactions, which could be catalyzed by transition metals. Soon after, the field was dominated by application of catalysts containing precious-metal centers leading to the facile synthesis of higher molecules. Significant role of transition metals in chemistry was highlighted by Nobel prizes in 2001 (K. B. Sharpless, W. S. Knowles, R. Noyori) for metal-catalyzed enantioselective hydrogenation and oxidation reactions, in 2005 (R. Schrock, R. Grubbs, Y. Chauvin) for application of transition metals in metathesis and in 2010 (R. F. Heck, A. Suzuki, E. Negishi) for application of Pd-based systems in cross-coupling reactions, which with enormous impact modernized organic synthesis in research laboratories and in industry. However, the application of late and noble metal catalytic systems exhibits crucial drawbacks. Noble metals are expensive, due to their low abundance in the earth crust (Figure 1)[4] and related challenges in their extraction. Moreover, they are toxic and lead to formation of toxic waste. Taking into account the huge impact of catalysis nowadays and how it can influence our life and environment, modern chemical society focuses on finding more economically and environmentally friendly methods. As an alternative, implementation of base metal catalysis gained a lot of attention as it can lead to most cost-effective and more environmentally friendly protocols. Moreover, base metals can demonstrate similar reactivity as noble metals or exhibit new features, leading to other interesting transformations.

DKK 445.00
1

ODNP enhanced NMR relaxometry and diffusometry - Dr Till Uberruck - Bog - Verlag G. Mainz - Plusbog.dk

ODNP enhanced NMR relaxometry and diffusometry - Dr Till Uberruck - Bog - Verlag G. Mainz - Plusbog.dk

In nuclear magnetic resonance (NMR) the demand for compact, low-cost instruments that can substitute expensive superconducting magnets is growing. Although compact NMR devices based on permanent magnets that can resolve 1H chemical shift differences are commercially available, the magnetic field strength of these devices is limited, which sets boundaries to the signal intensity and quality. Hyperpolarization techniques to boost the NMR signal beyond ist thermally given polarization are well known and applied on superconducting magnets. Thus, implementing these methods on compact NMR instruments will be the next step of development to gain an increased signal quality and widen the range of applications for those magnets. One part of this thesis deals with the development of compact magnets for an X-Band Overhauser Dynamic Nuclear Polarization (ODNP) setup and the construction of the hyperpolarization hardware itself. Two concepts of small open-access magnets are presented, simulated, and experimentally tested that allow a direct shimming of the magnetic field by displacing magnet blocks without the need of further pole shoes or shim pieces. The superior design is transferred to a bigger magnet, which can fit EPR resonators and is the center piece of the ODNP hardware. For this hardware an ODNP amplification board is constructed and a commercially purchased EPR resonator is modified to include NMR coils. All components are adjusted to each other, the communication between them is established and the basic functionality of the hardware demonstrated. Additionally to the hardware construction, a fast field mapping method is introduced to characterize the detection volume of compact NMR devices. This method facilitates the characterization and hence construction of permanent NMR magnets and saves about one order of magnitude in measurement time compared to the established procedures. Beside the construction of compact hyperpolarization setups, new applications areas for these techniques should be explored. In this context the idea of ODNP enhanced Laplace NMR experiments is explained and experimentally demonstrated by CPMG, inversion recovery, and PFG diffusion experiments on a model sample. Furthermore, these techniques are applied to study the influence of ODNP spin probes on the dynamic properties of Nafion membranes. Since ODNP relies on the presence of paramagnetic spin probes their influence on the material properties must be studied before any conclusion on material properties can be drawn from hyperpolarization experiments. A cornucopia of established and novel methods is applied to dissect Nafion properties in the presence of spin probes ranging from Small Angle X-ray Scattering (SAXS), Thermal Gravimetric Analysis (TGA), conductivity measurements, PFG NMR diffusometry, field cycling NMR relaxometry, ODNP relaxometry to Electron Paramagnetic Resonance (EPR), and new combinations thereof.

DKK 460.00
1