Paleomagnetic record of Site 177-1089

We report geomagnetic directional paleosecular variation, relative paleointensity proxies and oxygen isotope data from the upper 88 m composite depth (mcd) at South Atlantic Ocean Drilling Program (ODP) Site 1089 (40°56.2?S, 9°53.64?E, 4620 m water depth). The age model is provided by high-resolution oxygen isotope stratigraphy, augmented by radiocarbon dates from the upper 8 mcd of nearby piston core RC11-83. Mean sedimentation rates at Site 1089 are in the range of 15 to 20 cm/kyr. Two intervals during the Brunhes Chron, at ?29.6 mcd (?190 ka) and at ?48 mcd (?335 ka), have component magnetization directions with positive (reverse polarity) inclination; however, the excursional directions are heavily overprinted by the postexcursional field. Magnetite is the dominant carrier of magnetic remanence, and occurs in the pseudosingle-domain (PSD) grain size. An additional higher-coercivity magnetic carrier, characterized by low unblocking temperatures (<350°C), is assumed to be authigenic pyrrhotite. A decrease in magnetization intensity down core is mirrored by a reduction in pore water sulfate, indicating diagenetic reduction of magnetite. Despite down-core changes in magnetic mineralogy, normalized intensity records from Site 1089 are comparable with high-resolution paleointensity records from the North Atlantic (e.g., ODP Sites 983 and 984). Sediment properties and sedimentation patterns within the Cape (Site 1089) and Iceland (Sites 983 and 984) Basins are distinctly different at both millennial and orbital timescales and therefore preclude lithologic variability from being the source of this correlation. Variations in normalized intensity from Site 1089 therefore appear to reflect changes in global-scale geomagnetic field intensity.

Temperature-dependent sex ratio in a bird

To our knowledge, there is, so far, no evidence that incubation temperature can affect sex ratios in birds, although this is common in reptiles. Here, we show that incubation temperature does affect sex ratios in megapodes, which are exceptional among birds because they use environmental heat sources for incubation. In the Australian brush-turkey Alectura lathami, a mound-building megapode, more males hatch at low incubation temperatures and more females hatch at high temperatures, whereas the proportion is 1 : 1 at the average temperature found in natural mounds. Chicks from lower temperatures weigh less, which probably affects offspring survival, but are not smaller. Megapodes possess heteromorphic sex chromosomes like other birds, which eliminates temperature-dependent sex determination, as described for reptiles, as the mechanism behind the skewed sex ratios at high and low temperatures. Instead, our data suggest a sex-biased temperature-sensitive embryo mortality because mortality was greater at the lower and higher temperatures, and minimal at the middle temperature where the sex ratio was 1 : 1.

Strong electronic correlations in superconducting organic charge transfer salts

We review the role of strong electronic correlations in quasi-two-dimensional organic charge transfer salts such as (BEDT-TTF)(2)X, (BETS)(2)Y, and beta'-[Pd(dmit)(2)](2)Z. We begin by defining minimal models for these materials. It is necessary to identify two classes of material: the first class is strongly dimerized and is described by a half-filled Hubbard model; the second class is not strongly dimerized and is described by a quarter-filled extended Hubbard model. We argue that these models capture the essential physics of these materials. We explore the phase diagram of the half-filled quasi-two-dimensional organic charge transfer salts, focusing on the metallic and superconducting phases. We review work showing that the metallic phase, which has both Fermi liquid and 'bad metal' regimes, is described both quantitatively and qualitatively by dynamical mean field theory (DMFT). The phenomenology of the superconducting state is still a matter of contention. We critically review the experimental situation, focusing on the key experimental results that may distinguish between rival theories of superconductivity, particularly probes of the pairing symmetry and measurements of the superfluid stiffness. We then discuss some strongly correlated theories of superconductivity, in particular the resonating valence bond (RVB) theory of superconductivity. We conclude by discussing some of the major challenges currently facing the field. These include parameterizing minimal models, the evidence for a pseudogap from nuclear magnetic resonance (NMR) experiments, superconductors with low critical temperatures and extremely small superfluid stiffnesses, the possible spin- liquid states in kappa-(ET)(2)Cu-2(CN)(3) and beta'-[Pd(dmit)(2)](2)Z, and the need for high quality large single crystals.

Flow patterns, performance and scale-up of distillation trays

This work is concerned with the nature of liquid flow across industrial sieve trays operating in the spray, mixed, and the emulsified flow regimes. In order to overcome the practical difficulties of removing many samples from a commercial tray, the mass transfer process was investigated in an air water simulator column by heat transfer analogy. The temperature of the warm water was measured by many thermocouples as the water flowed across the single pass 1.2 m diameter sieve tray. The thermocouples were linked to a mini computer for the storage of the data. The temperature data were then transferred to a main frame computer to generate temperature profiles - analogous to concentration profiles. A comprehensive study of the existing tray efficiency models was carried out using computerised numerical solutions. The calculated results were compared with experimental results published by the Fractionation Research Incorporation (FRl) and the existing models did not show any agreement with the experimental results. Only the Porter and Lockett model showed a reasonable agreement with the experimental results for cenain tray efficiency values. A rectangular active section tray was constructed and tested to establish the channelling effect and the result of its effect on circular tray designs. The developed flow patterns showed predominantly flat profiles and some indication of significant liquid flow through the central region of the tray. This comfirms that the rectangular tray configuration might not be a satisfactory solution for liquid maldistribution on sieve trays. For a typical industrial tray the flow of liquid as it crosses the tray from the inlet to the outlet weir could be affected by the mixing of liquid by the eddy, momentum and the weir shape in the axial or the transverse direction or both. Conventional U-shape profiles were developed when the operating conditions were such that the froth dispersion was in the mixed regime, with good liquid temperature distribution while in the spray regime. For the 12.5 mm hole diameter tray the constant temperature profiles were found to be in the axial direction while in the spray regime and in the transverse direction for the 4.5 mm hole tray. It was observed that the extent of the liquid stagnant zones at the sides of the tray depended on the tray hole diameter and was larger for the 4.5 mm hole tray. The liquid hold-up results show a high liquid hold-up at the areas of the tray with low liquid temperatures, this supports the doubts about the assumptions of constant point efficiency across an operating tray. Liquid flow over the outlet weir showed more liquid flow at the centre of the tray at high liquid loading with low liquid flow at both ends of the weir. The calculated results of the point and tray efficiency model showed a general increase in the calculated point and tray efficiencies with an increase in the weir loading, as the flow regime changed from the spray to the mixed regime the point and the tray efficiencies increased from approximately 30 to 80%.Through the mixed flow regime the efficiencies were found to remain fairly constant, and as the operating conditions were changed to maintain an emulsified flow regime there was a decrease in the resulting efficiencies. The results of the estimated coefficient of mixing for the small and large hole diameter trays show that the extent of liquid mixing on an operating tray generally increased with increasing capacity factor, but decreased with increasing weir loads. This demonstrates that above certain weir loads, the effect of eddy diffusion mechanism on the process of liquid mixing on an operating tray to be negligible.

Pyrolysis and gasification of biomass and acid hydrolysis residues

This research was carried for an EC supported project that aimed to produce ethyl levulinate as a diesel miscible biofuel from biomass by acid hydrolysis. The objective of this research was to explore thermal conversion technologies to recover further diesel miscible biofuels and/or other valuable products from the remaining solid acid hydrolysis residues (AHR). AHR consists of mainly lignin and humins and contains up to 80% of the original energy in the biomass. Fast pyrolysis and pyrolytic gasification of this low volatile content AHR was unsuccessful. However, successful air gasification of AHR gave a low heating value gas for use in engines for power or heat with the aim of producing all the utility requirements in any commercial implementation of the ethyl levulinate production process. In addition, successful fast pyrolysis of the original biomass gave organic liquid yields of up to 63.9 wt.% (dry feed basis) comparable to results achieved using a standard hardwood. The fast pyrolysis liquid can be used as a fuel or upgraded to biofuels. A novel molybdenum carbide catalyst was tested in fast pyrolysis to explore the potential for upgrading. Although there was no deoxygenation, some bio-oil properties were improved including viscosity, pH and homogeneity through decreasing sugars and increasing furanics and phenolics. AHR gasification was explored in a batch gasifier with a comparison with the original biomass. Refractory and low volatile content AHR gave relatively low gas yields (74.21 wt.%), low tar yields (5.27 wt.%) and high solid yields (20.52 wt.%). Air gasification gave gas heating values of around 5MJ/NM3, which is a typical value, but limitations of the equipment available restricted the extent of process and product analysis. In order to improve robustness of AHR powder for screw feeding into gasifiers, a new densification technique was developed based on mixing powder with bio-oil and curing the mixture at 150°C to polymerise the bio-oil.

The deoxidation of steel with simple and complex deoxidisers

The deoxidation of steel with complex deoxidisers was studied at 1550°C and compared with silicon, aluminium and silicon/aluminium alloys as standards. The deoxidation alloy systems, Ca/Si/Al, Mg/Si/Al and Mn/Si/Al, were chosen for the low liquidus temperatures of many of their oxide mixtures and the potential deoxidising power of their constituent elements. Product separation rates and compositional relationships following deoxidation were examined. Silicon/aluminium alloy deoxidation resulted in the product compositions and residual oxygen contents expected from equilibrium and stoichiometric considerations, but with the Ca/Si/Al and Mg/Si/Al alloys the volatility of calcium and magnesium prevented them participating in the final solute equilibrium, despite their reported solubility in liquid iron. Electron-probe microanalysis of the products showed various concentrations of lime and magnesia, possibly resulting from reaction between the metal vapours and dissolved oxygen.The consequent reduction of silica activity in the products due to the presence of CaO and hgO produced an indirect effect of calcium and magnesium on the residual oxygen content. Product separation rates, indicated by vacuum fusion analyses, were not significantly influenced by calcium and magnesium but the rapid separation of products having a high Al2O3Si02 ratio was confirmed. Manganese participated in deoxidation, when present either as an alloying element in the steel or as a deoxidation alloy constituent. The compositions of initial oxide products were related to deoxidation alloy compositions. Separated products which were not alumina saturated, dissolved crucible material to achieve saturation. The melt equilibrated with this slag and crucible by diffusion to determine the residual oxygen content. MnO and SiO2 activities were calculated, and the approximate values of MnO deduced for the compositions obtained. Separation rates were greater for products of high interfacial tension. The rates calculated from a model based on Stoke's Law, showed qualitative agreement with experimental data when corrected for coalescence effects.

Residual stress effects during near-threshold fatigue crack growth

The fatigue crack propagation behaviour of a low alloy, boron-containing steel has been examined after austenitizing at 900°C or 1250°C and tempering at a range of temperatures up to 400°C. Fatigue threshold values were found to vary with austenitizing and tempering treatment in a range between 3.3 to 6 MPa √m when tested at a stress ratio (R) of 0.2. Crack propagation rates in the Paris regime were insensitive to heat treatment variations. The crack propagation path was essentially transgranular in all conditions with small regions of intergranular facets appearing at growth rates around the knee of the da/dN vs ΔK curve. The crack front shape showed marked retardation in the centre of the specimen at low tempering temperatures. Experimental determinations and computer predictions of residual stress levels in the specimens indicated that this was due to a central residual compressive stress resulting from differential cooling rates and the volume change associated with the martensite transformation. The results are discussed in terms of microstructural and residual stress effects on fatigue behaviour. © 1987.

Aspects of 350 ºC (500 ºF) embrittlement in a CrMoV steel

A study has been made of the fracture modes associated with toughness minima, observed in notched impact tests at 173K, for a weldable CrMoV steel, quenched from different austenitising temperatures, and tempered in the range 300-900K. The fracture mode at 623K varied from 100% transgranular cleavage for an austenitising temperature of 1523K. The results are discussed in terms of mechanisms for 350 ºC embrittlement, such mechanisms require modification to allow for the difficulty of dissolving alloy carbides at low austenitising temperatures.

Thermal processing of miscanthus, sugarcane bagasse, sugarcane trash and their acid hydrolysis residues

The research presented in this thesis was developed as part of DIBANET, an EC funded project aiming to develop an energetically self-sustainable process for the production of diesel miscible biofuels (i.e. ethyl levulinate) via acid hydrolysis of selected biomass feedstocks. Three thermal conversion technologies, pyrolysis, gasification and combustion, were evaluated in the present work with the aim of recovering the energy stored in the acid hydrolysis solid residue (AHR). Mainly consisting of lignin and humins, the AHR can contain up to 80% of the energy in the original feedstock. Pyrolysis of AHR proved unsatisfactory, so attention focussed on gasification and combustion with the aim of producing heat and/or power to supply the energy demanded by the ethyl levulinate production process. A thermal processing rig consisting on a Laminar Entrained Flow Reactor (LEFR) equipped with solid and liquid collection and online gas analysis systems was designed and built to explore pyrolysis, gasification and air-blown combustion of AHR. Maximum liquid yield for pyrolysis of AHR was 30wt% with volatile conversion of 80%. Gas yield for AHR gasification was 78wt%, with 8wt% tar yields and conversion of volatiles close to 100%. 90wt% of the AHR was transformed into gas by combustion, with volatile conversions above 90%. 5volO2%-95vol%N2 gasification resulted in a nitrogen diluted, low heating value gas (2MJ/m3). Steam and oxygen-blown gasification of AHR were additionally investigated in a batch gasifier at KTH in Sweden. Steam promoted the formation of hydrogen (25vol%) and methane (14vol%) improving the gas heating value to 10MJ/m3, below the typical for steam gasification due to equipment limitations. Arrhenius kinetic parameters were calculated using data collected with the LEFR to provide reaction rate information for process design and optimisation. Activation energy (EA) and pre-exponential factor (ko in s-1) for pyrolysis (EA=80kJ/mol, lnko=14), gasification (EA=69kJ/mol, lnko=13) and combustion (EA=42kJ/mol, lnko=8) were calculated after linearly fitting the data using the random pore model. Kinetic parameters for pyrolysis and combustion were also determined by dynamic thermogravimetric analysis (TGA), including studies of the original biomass feedstocks for comparison. Results obtained by differential and integral isoconversional methods for activation energy determination were compared. Activation energy calculated by the Vyazovkin method was 103-204kJ/mol for pyrolysis of untreated feedstocks and 185-387kJ/mol for AHRs. Combustion activation energy was 138-163kJ/mol for biomass and 119-158 for AHRs. The non-linear least squares method was used to determine reaction model and pre-exponential factor. Pyrolysis and combustion of biomass were best modelled by a combination of third order reaction and 3 dimensional diffusion models, while AHR decomposed following the third order reaction for pyrolysis and the 3 dimensional diffusion for combustion.

Element characteristic tolerance for semi-batch fixed bed biomass pyrolysis

Biomass pyrolysis to bio-oil is one of the promising sustainable fuels. In this work, relation between biomass feedstock element characteristic and crude bio-oil production yield and lower heating value was explored. The element characteristics considered in this study include moisture, ash, fix carbon, volatile matter, C, H, N, O, S, cellulose, hemicellulose, and lignin content. A semi-batch fixed bed reactor was used for biomass pyrolysis with heating rate of 30 °C/min from room temperature to 600 °C and the reactor was held at 600 °C for 1 h before cooling down. Constant nitrogen flow (1bar) was provided for anaerobic condition. Sago and Napier glass were used in the study to create different element characteristic of feedstock by altering mixing ratio. Comparison between each element characteristic to crude bio-oil yield and low heating value was conducted. The result suggested potential key element characteristic for pyrolysis and provide a platform to access the feedstock element acceptance range.

The mosses of Terra Nova National Park, Eastern Newfoundland, a bryofloristic analysis and interpretation

The known moss flora of Terra Nova National Park, eastern Newfoundland, comp~ises 210 species. Eighty-two percent of the moss species occurring in Terra Nova are widespread or widespread-sporadic in Newfoundland. Other Newfoundland distributional elements present in the Terra Nova moss flora are the northwestern, southern, southeastern, and disjunct elements, but four of the mosses occurring in Terra Nova appear to belong to a previously unrecognized northeastern element of the Newfoundland flora. The majority (70.9%) of Terra Nova's mosses are of boreal affinity and are widely distributed in the North American coniferous forest belt. An additional 10.5 percent of the Terra Nova mosses are cosmopolitan while 9.5 percent are temperate and 4.8 percent are arctic-montane species. The remaining 4.3 percent of the mosses are of montane affinity, and disjunct between eastern and western North America. In Terra Nova, temperate species at their northern limit are concentrated in balsam fir stands, while arctic-montane species are restricted to exposed cliffs, scree slopes, and coastal exposures. Montane species are largely confined to exposed or freshwater habitats. Inability to tolerate high summer temperatures limits the distributions of both arctic-montane and montane species. In Terra Nova, species of differing phytogeographic affinities co-occur on cliffs and scree slopes. The microhabitat relationships of five selected species from such habitats were evaluated by Discriminant Functions Analysis and Multiple Regression Analysis. The five mosses have distinct and different microhabitats on cliffs and scree slopes in Terra Nova, and abundance of all but one is associated with variation in at least one microhabitat variable. Micro-distribution of Grimmia torquata, an arctic-montane species at its southern limit, appears to be deterJ]lined by sensitivity to high summer temperatures. Both southern mosses at their northern limit (Aulacomnium androgynum, Isothecium myosuroides) appear to be limited by water availability and, possibly, by low winter temperatures. The two species whose distributions extend both north and south or the study area (Encalypta procera, Eurhynchium pulchellum) show no clear relationship with microclimate. Dispersal factors have played a significant role in the development of the Terra Nova moss flora. Compared to the most likely colonizing source (i .e. the rest of the island of Newfoundland), species with small diaspores have colonized the study area to a proportionately much greater extent than have species with large diaspores. Hierarchical log-linear analysis indicates that this is so for all affinity groups present in Terra Nova. The apparent dispersal effects emphasize the comparatively recent glaciation of the area, and may also have been enhanced by anthropogenic influences. The restriction of some species to specific habitats, or to narrowly defined microhabitats, appears to strengthen selection for easily dispersed taxa.

X-Ray Diffraction Study of Boron Produced by Pyrolysis of Boron Tribromide

The goal of this research was to determine the composition of boron deposits produced by pyrolysis of boron tribromide, and to use the results to (a) determine the experimental conditions (reaction temperature, etc.) necessary to produce alpha-rhombohedral boron and (b) guide the development/refinement of the pyrolysis experiments such that large, high purity crystals of alpha-rhombohedral boron can be produced with consistency. Developing a method for producing large, high purity alpha-rhombohedral boron crystals is of interest because such crystals could potentially be used to achieve an alpha-rhombohedral boron based neutron detector design (a solid-state detector) that could serve as an alternative to existing neutron detector technologies. The supply of neutron detectors in the United States has been hampered for a number of years due to the current shortage of helium-3 (a gas used in many existing neutron detector technologies); the development of alternative neutron detector technology such as an alpha-rhombohedral boron based detector would help provide a more sustainable supply of neutron detectors in this country. In addition, the prospect/concept of an alpha-rhombohedral boron based neutron detector is attractive because it offers the possibility of achieving a design that is smaller, longer life, less power consuming, and potentially more sensitive than existing neutron detectors. The main difficulty associated with creating an alpha-rhombohedral boron based neutron detector is that producing large, high purity crystals of alpha-rhombohedral boron is extremely challenging. Past researchers have successfully made alpha-rhombohedral boron via a number of methods, but no one has developed a method for consistently producing large, high purity crystals. Alpha-rhombohedral boron is difficult to make because it is only stable at temperatures below around 1100-1200 °C, its formation is very sensitive to impurities, and the conditions necessary for its formation are not fully understood or agreed upon in the literature. In this research, the method of pyrolysis of boron tribromide (hydrogen reduction of boron tribromide) was used to deposit boron on a tantalum filament. The goal was to refine this method, or potentially use it in combination with a second method (amorphous boron crystallization), to the point where it is possible to grow large, high purity alpha-rhombohedral boron crystals with consistency. A pyrolysis apparatus was designed and built, and a number of trials were run to determine the conditions (reaction temperature, etc.) necessary for alpha-rhombohedral boron production. This work was focused on the x-ray diffraction analysis of the boron deposits; x-ray diffraction was performed on a number of samples to determine the types of boron (and other compounds) formed in each trial and to guide the choices of test conditions for subsequent trials. It was found that at low reaction temperatures (in the range of around 830-950 °C), amorphous boron was the primary form of boron produced. Reaction temperatures in the range of around 950-1000 °C yielded various combinations of crystalline boron and amorphous boron. In the first trial performed at a temperature of 950 °C, a mix of amorphous boron and alpha-rhombohedral boron was formed. Using a scanning electron microscope, it was possible to see small alpha-rhombohedral boron crystals (on the order of ~1 micron in size) embedded in the surface of the deposit. In subsequent trials carried out at reaction temperatures in the range of 950 °C – 1000 °C, it was found that various combinations of alpha-rhombohedral boron, beta-rhombohedral boron, and amorphous boron were produced; the results tended to be unpredictable (alpha-rhombohedral boron was not produced in every trial), and the factors leading to success/failure were difficult to pinpoint. These results illustrate how sensitive of a process producing alpha-rhombohedral boron can be, and indicate that further improvements to the test apparatus and test conditions (for example, higher purity/cleanliness) may be necessary to optimize the boron deposition. Although alpha-rhombohedral boron crystals of large size were not achieved, this research was successful in (a) developing a pyrolysis apparatus and test procedure that can serve as a platform for future testing, (b) determining reaction temperatures at which alpha-rhombohedral boron can form, and (c) developing a consistent process for analyzing the boron deposits and determining their composition. Further experimentation is necessary to achieve a pyrolysis apparatus and test procedure that can yield large alpha-rhombohedral boron crystals with consistency.

Greenlandic Inuit show genetic signatures of diet and climate adaptation

The indigenous people of Greenland, the Inuit, have lived for a long time in the extreme conditions of the Arctic, including low annual temperatures, and with a specialized diet rich in protein and fatty acids, particularly omega-3 polyunsaturated fatty acids (PUFAs). A scan of Inuit genomes for signatures of adaptation revealed signals at several loci, with the strongest signal located in a cluster of fatty acid desaturases that determine PUFA levels. The selected alleles are associated with multiple metabolic and anthropometric phenotypes and have large effect sizes for weight and height, with the effect on height replicated in Europeans. By analyzing membrane lipids, we found that the selected alleles modulate fatty acid composition, which may affect the regulation of growth hormones. Thus, the Inuit have genetic and physiological adaptations to a diet rich in PUFAs.

Origin and ecological selection of core and food-specific bacterial communities associated with meat and seafood spoilage

The microbial spoilage of meat and seafood products with short shelf lives is responsible for a significant amount of food waste. Food spoilage is a very heterogeneous process, involving the growth of various, poorly characterized bacterial communities. In this study, we conducted 16S ribosomal RNA gene pyrosequencing on 160 samples of fresh and spoiled foods to comparatively explore the bacterial communities associated with four meat products and four seafood products that are among the most consumed food items in Europe. We show that fresh products are contaminated in part by a microbiota similar to that found on the skin and in the gut of animals. However, this animal-derived microbiota was less prevalent and less abundant than a core microbiota, psychrotrophic in nature, mainly originated from the environment (water reservoirs). We clearly show that this core community found on meat and seafood products is the main reservoir of spoilage bacteria. We also show that storage conditions exert strong selective pressure on the initial microbiota: alpha diversity in fresh samples was 189 +/- 58 operational taxonomic units (OTUs) but dropped to 27 +/- 12 OTUs in spoiled samples. The OTU assemblage associated with spoilage was shaped by low storage temperatures, packaging and the nutritional value of the food matrix itself. These factors presumably act in tandem without any hierarchical pattern. Most notably, we were also able to identify putative new clades of dominant, previously undescribed bacteria occurring on spoiled seafood, a finding that emphasizes the importance of using culture-independent methods when studying food microbiota.

Synthesis, characterization and chemical vapor deposition of transition metal di(tert-butyl)amido compounds

Although the transition metal chemistry of many dialkylamido ligands has been well studied, the chemistry of the bulky di(tert-butyl)amido ligand has been largely overlooked. The di(tert-butyl)amido ligand is well suited for synthesizing transition metal compounds with low coordination numbers; such compounds may exhibit interesting structural, physical, and chemical properties. Di(tert-butyl)amido complexes of transition metals are expected to exhibit high volatilities and low decomposition temperatures, thus making them well suited for the chemical vapor deposition of metals and metal nitrides. Treatment of MnBr₂(THF)₂, FeI₂, CoBr₂(DME), or NiBr₂(DME) with two equivalents of LiN(t-Bu)2 in benzene affords the two-coordinate complex M[N(t-Bu)₂]₂, where M is Mn, Fe, Co, or Ni. Crystallographic studies show that the M-N distances decrease across the series: 1.9365 (Mn), 1.8790 (Fe), 1.845 (Co), 1.798 Å (Ni). The N-M- N angles are very close to linear for Mn and Fe (179.30 and 179.45°, respectively), but bent for Co and Ni (159.2 and 160.90°, respectively). As expected, the d⁵ Mn complex has a magnetic moment of 5.53 μΒ that is very close to the spin only value. The EPR spectrum is nearly axial with a low E/D ratio of 0.014. The d⁶ Fe compound has a room temperature magnetic moment of 5.55 μΒ indicative of a large orbital angular momentum contribution. It does not exhibit a Jahn-Teller distortion despite the expected doubly degenerate ground state. Applied field Mössbauer spectroscopy shows that the effective internal hyperfine field is unusually large, Hint = 105 T. The magnetic moments of Co[N(t-Bu)₂]₂ and Ni[N(t-Bu)₂]₂ are 5.24 and 3.02 μΒ respectively. Both are EPR silent at 4.2 K. Treatment of TiCl₄ with three equivalents of LiN(t-Bu)2 in pentane affords the briding imido compound Ti₂[μ-N(t-Bu)]₂Cl₂[N(t-Bu)₂]₂ via a dealkylation reaction. Rotation around the bis(tert-butyl)amido groups is hindered, with activation parameters of ΔH‡ = 12.8 ± 0.6 kcal mol-1 and ΔS‡ = -8 ± 2 cal K-1 ·mol-1, as evidenced by variable temperature 1H NMR spectroscopy. Treatment of TiCl₄ with two equivalents of HN(t-Bu)₂ affords Ti₂Cl₆[N(t-Bu)₂]₂. This complex shows a close-contact of 2.634(3) Å between Ti and the carbon atom of one of the CH₃ substituents on the tert-butyl groups. Theoretical considerations and detailed structural comparisons suggest this interaction is not agostic in nature, but rather is a consequence of interligand repulsions. Treatment of NiI₂(PPh3)₂ and PdCl₂(PPh₃)₂ with LiN(t-Bu)₂in benzene affords Ni[N(t-Bu)₂](PPh₃)I and Pd₃(μ₂-NBut₂)2(μ₂-PPh₂)Ph(PPh₃) respectively. The compound Ni[N(t-Bu)₂](PPh₃)I has distorted T-shape in geometry, whereas Pd₃(μ₂-NBut₂)₂(μ₂-PPh₂)Ph(PPh₃) contains a triangular palladium core. Manganese nitride films were grown from Mn[N(t-Bu)₂]₂ in the presence of anhydrous ammonia. The growth rate was several nanometers per minute even at the remarkably low temperature of 80⁰C. As grown, the films are carbon- and oxygen-free, and have a columnar morphology. The spacings between the columns become smaller and the films become smoother as the growth temperature is increased. The composition of the films is consistent with a stoichiometry of Mn₅N₂.