The design of an Fe-12Mn-O.2Ti alloy steel for low temperature use

An investigation was made to improve the low temperature mechanical properties of Fe-8 approximately 12% Mn-O 2Ti alloy steels. A two-phase(alpha + gamma) tempering in combination with cold working or hot working was identified as an effective treatment. A potential application as a Ni-free cryogenic steel was shown for this alloy. It was also shown that an Fe-8Mn steel could be grain-refined by a purely thermal treatment because of its dislocated martensitic structure and absence of epsilon phase. A significant reduction of the ductile-brittle transition temperature was obtained in this alloy. The nature and origin of brittle fracture in Fe-Mn alloys were also investigated. Two embrittling regions were found in a cooling curve of an Fe-12Mn-O 2Ti steel which was shown to be responsible for intergranular fracture. Auger electron spectroscopy identified no segregation during solution-annealing treatment. Avoiding the embrittling zones by controlled cooling led to a high cryogenic toughness in a solution-annealed condition

Two Dimensional Diluted Magnetic Semiconductor Systems

We develop a theory for two-dimensional diluted magnetic semiconductor systems (e.g. $\textrm{Ga}_{1-x}\textrm{Mn}_{x}\textrm{As}$ layers) where the itinerant carriers mediating the ferromagnetic interaction between the impurity local moments, as well as the local moments themselves, are confined in a two-dimensional layer. The theory includes exact spatial disorder effects associated with the random local moment positions within a disordered RKKY lattice field theory description. We predict the ferromagnetic transition temperature ($T_{c}$) as well as the nature of the spontaneous magnetization. The theory includes disorder and finite carrier mean free path effects as well as the important correction arising from the {\it finite temperature} RKKY interaction, finding a strong density dependence of $T_{c}$ in contrast to the simple virtual crystal approximation.Comment: New results added in connection with the Hohenberg-Mermin-Wagner theore

Solid State NMR Characterization of Complex Metal Hydrides systems for Hydrogen Storage Applications

Solid state NMR is widely applied in studies of solid state chemistries for hydrogen storage reactions. Use of ^(11)B MAS NMR in studies of metal borohydrides (BH_4) is mainly focused, revisiting the issue of dodecaborane formation and observation of ^(11)B{^1H} Nuclear Overhauser Effect

Stability and Reversibility of Lithium Borohydrides Doped by Metal Halides and Hydrides

In an effort to develop reversible metal borohydrides with high hydrogen storage capacities and low dehydriding temperature, doping LiBH4 with various metal halides and hydrides has been conducted. Several metal halides such as TiCl3, TiF3, and ZnF2 effectively reduced the dehydriding temperature through a cation exchange interaction. Some of the halide doped LiBH4 are partially reversible. The LiBH4 + 0.1TiF3 desorbed 3.5 wt % and 8.5 wt % hydrogen at 150 and 450 °C, respectively, with subsequent reabsorption of 6 wt % hydrogen at 500 °C and 70 bar observed. XRD and NMR analysis of the rehydrided samples confirmed the reformation of LiBH4. The existence of the (B12H12)−2 species in dehydrided and rehydrided samples gives insight into the resultant partial reversibility. A number of other halides, MgF2, MgCl2, CaCl2, SrCl2, and FeCl3, did not reduce the dehydriding temperature of LiBH4 significantly. XRD and TGA-RGA analyses indicated that an increasing proportion of halides such as TiCl3, TiF3, and ZnCl2 from 0.1 to 0.5 mol makes lithium borohydrides less stable and volatile. Although the less stable borohydrides such as LiBH4 + 0.5TiCl3, LiBH4 + 0.5TiF3, and LiBH4 + 0.5ZnCl2 release hydrogen at room temperature, they are not reversible due to unrecoverable boron loss caused by diborane emission. In most cases, doping that produced less stable borohydrides also reduced the reversible hydrogen uptake. It was also observed that halide doping changed the melting points and reduced air sensitivity of lithium borohydrides

Deuterium site occupancy and phase boundaries in ZrNiDx (0.87<=x<=3.0)

ZrNiDx samples with compositions between x=0.87 and x=3.0 were investigated by 2H magic-angle spinning nuclear magnetic resonance spectroscopy (MAS-NMR), powder x-ray diffraction (XRD), neutron vibrational spectroscopy (NVS), and neutron powder diffraction (NPD). The rigid-lattice MAS-NMR spectrum for a ZrNiD0.88 sample in the triclinic beta phase shows a single phase with two well-resolved resonances at +11.5 and −1.7 ppm, indicating that two inequivalent D sites are occupied, as was observed previously in ZrNiD1.0. For ZrNiD0.88, the ratio of spectral intensities of the two lines is 1:0.76, indicating that the D site corresponding to the +11.5 ppm line has the lower site energy and is fully occupied. Similarly, the neutron vibrational spectra for ZrNiD0.88 clearly confirm that at least two sites are occupied. For ZrNiD1.0, XRD indicates that ~5% of the metal atoms are in the gamma phase, corresponding to an upper composition for the beta phase of x=0.90±0.04, consistent with the MAS-NMR and neutron vibrational spectra indicating that x=0.88 is single phase. The MAS-NMR and NVS of ZrNiD1.87 indicate a mixed-phase sample (beta+gamma) and clearly show that the two inequivalent sites observed at x=0.88 cannot be attributed to the sites normally occupied in the gamma phase. For ZrNiD2.75, NPD results indicate a gamma-phase boundary of x=2.86±0.03 at 300 K, increasing to 2.93±0.02 at 180 K and below, in general agreement with the phase boundary estimated from the NVS and MAS-NMR spectra of ZrNiD1.87. Rigid-lattice 2H MAS-NMR spectra of ZrNiD2.75 and ZrNiD2.99 show a ratio of spectral intensities of 1.8±0.1:1 and 2.1±0.1:1 (Zr3Ni:Zr3Ni2), respectively, indicating complete occupancy of the lower-energy Zr3Ni2 site, consistent with the NPD results. For each composition, the correlation time for deuterium hopping was determined at the temperature where resolved peaks in the MAS-NMR spectrum coalesce due to motion between inequivalent D sites. The measured correlation times are consistent with previously determined motional parameters for ZrNiHx

Hydrogenation of Magnesium Nickel Boride for Reversible Hydrogen Storage

We report that a ternary magnesium nickel boride (MgNi_(2.5)B_2) mixed with LiH and MgH_2 can be hydrogenated reversibly forming LiBH_4 and Mg_2NiH_4 at temperatures below 300 °C. The ternary boride was prepared by sintering a mechanically milled mixture of MgB_2 and Ni precursors at 975 °C under inert atmosphere. Hydrogenation of the ternary, milled with LiH and MgH_2, was performed under 100 to 160 bar H_2 at temperatures up to 350 °C. Analysis using X-ray diffraction, Fourier transform infrared, and ^(11)B magic angle spinning NMR confirmed that the ternary boride was hydrogenated forming borohydride anions. The reaction was reversible with hydrogenation kinetics that improved over three cycles. This work suggests that there may be other ternary or higher order boride phases useful for reversible hydrogen storage