Additive manufacturing of multi-material parts – Design guidelines for manufacturing of 316L/CuCrZr in laser powder bed fusion

Additive manufacturing (AM) can be used to produce multi-material parts in which the material can be varied voxel-wise in all three spatial directions. This means that the paradigm of the homogeneous material can be abandoned and local effects such as heat conduction or damping can be selectively adjusted in the part. Recently, continuous development of machine technology has allowed the production of multi-metal materials in laser powder bed fusion (PBF-LB/MM). Compared to other additive manufacturing processes for multi-material production, this allows greater design freedom and detail accuracy to be realized. However, due to the novel character of multi-material manufacturing in PBF-LB, the process knowledge for successful and reproducible fabrication is currently lacking. This paper focuses on establishing design guidelines for manufacturing the material pairing of stainless steel 316L (1.4404) and copper alloy CuCrZr (CW106C). The article is accompanied by the development of a specific process chain. As a result of this work, design guidelines for multi-material parts are available for the first time, in regard to arrangement, size, overhangs, economy, powder quality and laser scanning

Additive Manufacturing of Metallic Multi-Material Parts: Local Conductivity Adjustment through Functionally Graded Material Transitions of 316L and CuCrZr

Recently, powder bed-based additive manufacturing has made it possible to produce metallic multi-material parts where the material can be varied within the build plane voxel by voxel. This capability enables the realization of functionally graded materials for selective adjustment of local part properties, such as heat dissipation. In this study, the effect of location-dependent property adjustment using functionally graded materials is investigated for the combination of 316L and CuCrZr in terms of conductivity. Functionally graded test specimens were successfully produced with voxel sizes of 1 mm and 2 mm, demonstrating the influence of geometry-dependent material gradients on conductivity properties. Additionally, the study reveals a significant improvement in conductivity of CuCrZr by a factor of more than 4 following heat treatment. Nevertheless, the resolution of the gradient is limited by the manufacturing facility in terms of the minimum possible voxel size

Multi-material laser powder bed fusion additive manufacturing of concentrated wound stator teeth

Additive manufacturing using Powder Bed Fusion by Laser Beam (PBF-LB) enables products with high design freedom. In addition, the ability to process more than one material in all three spatial directions makes it possible to produce highly functional components in one single process. This article investigates whether multi-material manufacturing using PBF-LB is suitable for producing coils for electric motors, which are designed with integrated cooling channels to increase the power density. For this purpose, the copper alloy CuCr1Zr for the coils and the stainless steel 1.4404 (316L) for the core are processed simultaneously. The component designs were verified using 2D and 3D finite element analysis and then manufactured in a multi-material PBF-LB process. While good electrical conductivity of the copper alloy was achieved by heat treatment, it was found that thermal distortion caused deviations from the nominal geometry. The measurement of the electrical properties showed that this distortion leads to short-circuit currents within the coils and the teeth. On this basis, ideas for solutions were developed, with the help of which the functionality of the coils can be ensured or the power density can also be increased. In addition to adapting the design of the component, this includes processing additional or other materials, such as soft magnetic composites

Global CO2 fertilization of Sphagnum peat mosses via suppression of photorespiration during the twentieth century

Natural peatlands contribute significantly to global carbon sequestration and storage of biomass, most of which derives from Sphagnum peat mosses. Atmospheric CO2 levels have increased dramatically during the twentieth century, from 280 to > 400 ppm, which has affected plant carbon dynamics. Net carbon assimilation is strongly reduced by photorespiration, a process that depends on the CO2 to O-2 ratio. Here we investigate the response of the photorespiration to photosynthesis ratio in Sphagnum mosses to recent CO2 increases by comparing deuterium isotopomers of historical and contemporary Sphagnum tissues collected from 36 peat cores from five continents. Rising CO2 levels generally suppressed photorespiration relative to photosynthesis but the magnitude of suppression depended on the current water table depth. By estimating the changes in water table depth, temperature, and precipitation during the twentieth century, we excluded potential effects of these climate parameters on the observed isotopomer responses. Further, we showed that the photorespiration to photosynthesis ratio varied between Sphagnum subgenera, indicating differences in their photosynthetic capacity. The global suppression of photorespiration in Sphagnum suggests an increased net primary production potential in response to the ongoing rise in atmospheric CO2, in particular for mire structures with intermediate water table depths

NMR studies of metabolites and xenobiotics : From time-points to long-term metabolic regulation

Chemical species carry information in two dimensions, in their concentrations and their isotopic signatures. The concentrations of metabolites or synthetic compounds describe the composition of a chemical or biological system, while isotopic signatures describe processes in the system by their reaction pathways, regulation, and responses to external stimuli. Stable isotopes are unique tracers of these processes because their natural abundances are modulated by isotope effects occurring in physical processes as well as in chemical reactions. Nuclear magnetic resonance (NMR) spectroscopy is a prime technique not only for identification and quantification of small molecules in complex systems but also for measuring intramolecular distribution of stable isotopes in metabolites and other small molecules. In this thesis, we use quantitative NMR in three fields: in food science, environmental pollutant tracing, and plant-climate science. The phospholipid (PL) composition of food samples is of high interest because of their nutritional value and technological properties. However, the analysis of PLs is difficult as they constitute only a small fraction of the total lipid contents in foods. Here, we developed a method to identify PLs and determine their composition in food samples, by combining a liquid-liquid extraction approach for enriching PLs, with specialized 31P,1H-COSY NMR experiments to identify and quantify PLs. Wide-spread pollution with synthetic compounds threatens the environment and human health. However, the fate of pollutants in the environment is often poorly understood. Using quantitative deuterium NMR spectroscopy, we showed for the nitrosamine NDMA and the pesticide DDT how intramolecular distributions (isotopomer patterns) of the heavy hydrogen isotope deuterium reveal mechanistic insight into transformation pathways of pollutants and organic compounds in general. Intramolecular isotope distributions can be used to trace a pollutant’s origin, to understand its environmental transformation pathways and to evaluate remediation approaches. The atmospheric CO2 concentration ([CO2]) is currently rising at an unprecedented rate and plant responses to this increase in [CO2] influence the global carbon cycle and will determine future plant productivity. To investigate long-term plant responses, we developed a method to elucidate metabolic fluxes from intramolecular deuterium distributions of metabolites that can be extracted from historic plant material. We show that the intramolecular deuterium distribution of plant glucose depends on growth [CO2] and reflects the magnitude of photorespiration, an important side reaction of photosynthesis. In historic plant samples, we observe that photorespiration decreased in annual crop plants and natural vegetation over the past century, with no observable acclimation, implying that photosynthesis increased. In tree-ring samples from all continents covering the past 60 – 700 years, we detected a significantly smaller decrease in photorespiration than expected. We conclude that the expected “CO2 fertilization” has occurred but was significantly less pronounced in trees, due to opposing effects. The presented applications show that intramolecular isotope distributions not only provide information about the origin and turnover of compounds but also about metabolic regulation. By extracting isotope distributions from archives of plant material, metabolic information can be obtained retrospectively, which allows studies over decades to millennia, timescales that are inaccessible with manipulation experiments

Additive manufacturing of multi-material parts – Design guidelines for manufacturing of 316L/CuCrZr in laser powder bed fusion

Additive manufacturing (AM) can be used to produce multi-material parts in which the material can be varied voxel-wise in all three spatial directions. This means that the paradigm of the homogeneous material can be abandoned and local effects such as heat conduction or damping can be selectively adjusted in the part. Recently, continuous development of machine technology has allowed the production of multi-metal materials in laser powder bed fusion (PBF-LB/MM). Compared to other additive manufacturing processes for multi-material production, this allows greater design freedom and detail accuracy to be realized. However, due to the novel character of multi-material manufacturing in PBF-LB, the process knowledge for successful and reproducible fabrication is currently lacking. This paper focuses on establishing design guidelines for manufacturing the material pairing of stainless steel 316L (1.4404) and copper alloy CuCrZr (CW106C). The article is accompanied by the development of a specific process chain. As a result of this work, design guidelines for multi-material parts are available for the first time, in regard to arrangement, size, overhangs, economy, powder quality and laser scanning

Elucidating Turnover Pathways of Bioactive Small Molecules by Isotopomer Analysis : The Persistent Organic Pollutant DDT

The persistent organic pollutant DDT (1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane) is still indispensable in the fight againstmalaria, although DDT and related compounds  pose toxicological  hazards. Technical DDT contains the dichloro congenerDDD (1-chloro-4-[2,2-dichloro-1-(4-chlorophenyl)ethyl]benzene)   as by-product, but  DDD is also formed by  reductive degradation of DDT in the environment. To differentiate between DDD formation pathways, we applied deuterium NMR spectroscopy to measure intramolecular deuterium distributions (2H isotopomer abundances) of DDT and DDD. DDD formed in the technical  DDT synthesis was strongly deuterium-enriched at one intramolecular position, which we traced back to 2H/1H fractionation of a chlorination step in the technical synthesis.  In contrast, DDD formed by reductive degradation was strongly depleted at the same position, which was due to the incorporation of 2H-depleted hydride equivalents during reductive degradation. Thus, intramolecular isotope distributions give mechanistic information on reaction pathways, and explain a puzzling difference in the whole-molecule 2H/1H ratio between DDT and DDD. In general, our results highlight that intramolecular isotope distributions are essential to interpret whole-molecule isotope ratios. Intramolecular isotope information allows distinguishing pathways of DDD formation, which is important to identify polluters or to assess  DDT turnover in the environment. Because  intramolecular isotope data directly reflect isotope fractionation of individual chemical reactions, they are broadly applicable to elucidate transformation pathways of smallbioactive molecules in chemistry, physiology and environmental science

Tree-ring cellulose exhibits several interannual 13C signals on the intramolecular level

Measurements of carbon isotope contents (13C/12C, δ 13C) in tree rings provide retrospective information about the short and long-term dynamics of plant ecophysiological, and paleo-environmental traits. They are commonly based on 13C/12C ratios of cellulose, and interpreted with respect to fractionation related to CO2 diffusion into plants and its fixation by Rubisco (diffusion-Rubisco - DR - fractionation). However, primary metabolites such as glucose are known to exhibit intramolecular 13C/12C differences of the order of 10h which reflect 13C fractionation by enzyme reactions downstream of Rubisco (Post-Rubisco - PR - fractionation). PR fractionation is not commonly considered in dendrochronological studies. It has not yet been investigated whether glucose monomers of cellulose show intramolecular 13C differences. Furthermore, it is unknown whether PR fractionation varies among years, and whether DR and PR fractionations introduce distinct 13C/12C signals. To test this, we isolated the glucose monomers of Pinus nigra tree rings, and determined 13C/12C ratios of all intramolecular glucose carbon positions by quantitative 13C NMR. The resulting dataset consists of 6 time series of positional 13C/12C ratios with annual resolution, extending from 1961 to 1995. Tree-ring glucose exhibits intramolecular 13C/12C differences of the order of 10h. Cluster analysis revealed several independent intramolecular 13C signals. These signals constitute distinct channels of information about both the DR interface and associated environmental triggers, as well as PR processes related to downstream C allocation. Thus, analysis of intramolecular 13C signals can extract more information with better quality from tree rings. This might enhance our understanding of biogeochemical, ecophysiological and paleo-environmental phenomena

Tree-ring cellulose exhibits several interannual 13C signals on the intramolecular level

Measurements of carbon isotope contents (13C/12C, δ 13C) in tree rings provide retrospective information about the short and long-term dynamics of plant ecophysiological, and paleo-environmental traits. They are commonly based on 13C/12C ratios of cellulose, and interpreted with respect to fractionation related to CO2 diffusion into plants and its fixation by Rubisco (diffusion-Rubisco - DR - fractionation). However, primary metabolites such as glucose are known to exhibit intramolecular 13C/12C differences of the order of 10h which reflect 13C fractionation by enzyme reactions downstream of Rubisco (Post-Rubisco - PR - fractionation). PR fractionation is not commonly considered in dendrochronological studies. It has not yet been investigated whether glucose monomers of cellulose show intramolecular 13C differences. Furthermore, it is unknown whether PR fractionation varies among years, and whether DR and PR fractionations introduce distinct 13C/12C signals. To test this, we isolated the glucose monomers of Pinus nigra tree rings, and determined 13C/12C ratios of all intramolecular glucose carbon positions by quantitative 13C NMR. The resulting dataset consists of 6 time series of positional 13C/12C ratios with annual resolution, extending from 1961 to 1995. Tree-ring glucose exhibits intramolecular 13C/12C differences of the order of 10h. Cluster analysis revealed several independent intramolecular 13C signals. These signals constitute distinct channels of information about both the DR interface and associated environmental triggers, as well as PR processes related to downstream C allocation. Thus, analysis of intramolecular 13C signals can extract more information with better quality from tree rings. This might enhance our understanding of biogeochemical, ecophysiological and paleo-environmental phenomena

Intramolecular stable isotope variation : Consequences for conventional isotope measurements and elucidation of new ecophysiological signals

Isotope ratios (13C/12C and 2H/1H) have long been used in plant ecophysiology and for reconstruction of environmental variables. For decades it has also been known that heavy isotopes are distributed unevenly IN biological metabolites. In other words, the isotopomers of metabolites have unequal abundances. Consequently, conventional δ values are whole-molecule averages over varying intramolecular values. However, this biochemical knowledge has not been applied in plant ecophysiology or biogeochemistry, because the first measurements of intramolecular isotope distributions were extremely cumbersome, requiring breakdown of metabolites into small molecules and IRMS measurements on those. Since then, NMR methodology has advanced so that intramolecular isotope distributions can routinely be measured (Chaintreau et al., Anal. Chim. Acta 2013), although large samples are needed. Here we demonstrate the importance of intramolecular isotope distributions with several examples. 1. We show that 13C is distributed unevenly in tree-ring cellulose. While this is not surprising given previous observations, it has important consequences: When wood enters soil organic matter and is broken down, the δ13C of respired CO2 will only follow δ13C of cellulose if the glucose units are fully respired. If part of the glucose molecules enters other pathways, such as the oxidative pentose phosphate pathway, δ13C of liberated CO2 can deviate markedly from the whole-molecule value. This may have consequences for using δ13C of CO2 to unravel ecosystem C exchange fluxes. 2. Intramolecular isotope distributions are created by enzyme isotope effects, hence they constitute fingerprints of biosynthetic pathways and can report on regulation of metabolism on time scales up to millennia. As particular advantage, this information can be encoded in ratios of isotopomer abundances (Augusti et al., Chem. Geol. 2008), and can be extracted independent of the isotope ratio of the whole molecule, and of the isotope source (Ehlers et al., PNAS 2015). 3. We demonstrate that intramolecular 13C distributions of the glucose units of tree-ring cellulose vary over time. This implies that 13C fractionations mechanisms beyond the well-known stomata-Rubisco mechanism exist. The time-dependent intramolecular variation constitutes new ecophysiological information. 4. When δ13C or δD are used as proxies for ecophysiological parameters, correlation coefficients between both quantities are restricted to low values, limiting the power of isotope-based reconstructions. We show that this limitation is at least partly caused by intramolecular isotope variation. Conversely, higher correlation coefficients can be observed between intramolecular isotope parameters – position-specific carbon isotope ratios or deuterium isotopomer ratios – and ecophysiological parameters. Thus, intramolecular isotope data allow for more powerful reconstructions of physiological and environmental parameter