Science and Technology Review December 2010

This month's issue has the following articles: (1) More Insight to Better Understand Climate Change - Commentary by Tomas Diaz de la Rubia; (2) Strengthening Our Understanding of Climate Change - Researchers at the Center for Accelerator Mass Spectrometry are working to better understand climate variation and sharpen the accuracy of predictive models; (3) Precision Diagnostics Tell All - The National Ignition Facility relies on sophisticated diagnostic instruments for measuring the key physical processes that occur in high-energy-density experiments; (4) Quick Detection of Pathogens by the Thousands - Livermore scientists have developed a device that can simultaneously identify thousands of viruses and bacteria within 24 hours; and (5) Carbon Dioxide into the Briny Deep - A proposed technique for burying carbon dioxide underground could help mitigate the effects of this greenhouse gas while producing freshwater

Three-dimensionally Ordered Macroporous Structure Enabled Nanothermite Membrane of Mn2O3/Al

Mn2O3 has been selected to realize nanothermite membrane for the first time in the literature. Mn2O3/Al nanothermite has been synthesized by magnetron sputtering a layer of Al film onto three-dimensionally ordered macroporous (3DOM) Mn2O3 skeleton. The energy release is significantly enhanced owing to the unusual 3DOM structure, which ensures Al and Mn2O3 to integrate compactly in nanoscale and greatly increase effective contact area. The morphology and DSC curve of the nanothermite membrane have been investigated at various aluminizing times. At the optimized aluminizing time of 30 min, energy release reaches a maximum of 2.09 kJ∙g−1, where the Al layer thickness plays a decisive role in the total energy release. This method possesses advantages of high compatibility with MEMS and can be applied to other nanothermite systems easily, which will make great contribution to little-known nanothermite research

Ambient-temperature Conditioning as a Probe of Double-C Transformation Mechanisms in Pu-2.0 at. % Ga

The gallium-stabilized Pu-2.0 at. % Ga alloy undergoes a partial or incomplete low-temperature martensitic transformation from the metastable {delta} phase to the gallium-containing, monoclinic {alpha}{prime} phase near -100 C. This transformation has been shown to occur isothermally and it displays anomalous double-C kinetics in a time-temperature-transformation (TTT) diagram, where two nose temperatures anchoring an upper- and lower-C describe minima in the time for the initiation of transformation. The underlying mechanisms responsible for the double-C behavior are currently unresolved, although recent experiments suggest that a conditioning treatment--wherein, following an anneal at 375 C, the sample is held at a sub-anneal temperature for a period of time--significantly influences the upper-C of the TTT diagram. As such, elucidating the effects of the conditioning treatment upon the {delta} {yields} {alpha}{prime} transformation can provide valuable insights into the fundamental mechanisms governing the double-C kinetics of the transition. Following a high-temperature anneal, a differential scanning calorimeter (DSC) was used to establish an optimal conditioning curve that depicts the amount of {alpha}{prime} formed during the transformation as a function of conditioning temperature for a specified time. With the optimal conditioning curve as a baseline, the DSC was used to explore the circumstances under which the effects of the conditioning treatment were destroyed, resulting in little or no transformation

Transmission Electron Microscopy Characterization of Helium Bubbles in Aged Plutonium

The self-irradiation damage generated by alpha decay of plutonium results in the formation of lattice defects, helium, and uranium atoms. Over time, microstructural evolution resulting from the self-irradiation may influence the physical and mechanical properties of the material. In order to assess microstructural changes, we have developed and applied procedures for the specimen preparation, handling, and transmission electron microscopy characterization of Pu alloys. These transmission electron microscopy investigations of Pu-Ga alloys ranging in age up to 42-years old reveal the presence of nanometer-sized helium bubbles. The number density of bubbles and the average size have been determined for eight different aged materials

Isothermal Martensitic and Pressure-Induced ? to ?? Phase Transformations in a Pu-Ga Alloy

A Pu-2 at.% Ga alloy specimen is slowly compressed to {approx}1 GPa in a large volume moissanite anvil cell to induce the face-centered cubic {delta} to simple monoclinic {alpha}{prime} phase transformation. Optical microscopy, x-ray diffraction, and transmission electron microscopy of the specimen recovered to ambient pressure reveal that the vast majority of the microstructure consists of the {alpha}{prime} phase with grain sizes ranging from 10 nm to several hundred nm, with the remainder being {delta} phase dispersed between the {alpha}{prime} grains. This morphology is in contrast to the transformation product of the low-temperature isothermal martensite in which the lath-shaped {alpha}{prime} particles are {approx}20 {micro}m by 2 {micro}m

Isothermal Martensitic and Pressure-Induced Delta to Alpha-Prime Phase Transformations in a Pu-Ga Alloy

A well-homogenized Pu-2 at.% Ga alloy can be retained in the metastable face-centered cubic {delta} phase at room temperature. Ultimately, this metastable {delta} phase will decompose via a eutectoid transformation to the thermodynamically stable monoclinic {alpha} phase and the intermetallic compound Pu{sub 3}Ga over a period of approximately 10,000 years [1]. In addition, these low solute-containing {delta}-phase Pu alloys are metastable with respect to an isothermal martensitic phase transformation to the {alpha}{prime} phase during low temperature excursions [2, 3] and are also metastable with respect to a {delta} {yields} {alpha}{prime} phase transformation with increases in pressure [3-5]. The low temperature {delta} {yields} {alpha}{prime} isothermal martensitic phase transformation in the Pu-2 at.% Ga alloy only goes to {approx}25% completion with the resultant {approx}20 {micro}m long by 2 {micro}m wide lath-shaped {alpha}{prime} particles dispersed within the {delta} matrix. In recently reported studies, Faure et al. [4] have observed a {delta} {yields} {gamma} {yields} {alpha}{prime} pressure-induced phase transformation sequence during a diamond anvil cell investigation and, based on x-ray diffraction and density and compressibility experiments, Harbur [5] has concluded that both {alpha}{prime} and an amorphous phase are present in samples that were pressurized and recovered. In this work, a large volume moissanite anvil cell is constructed to permit the pressurization and recovery of specimens of a size suitable for TEM and electron diffraction studies. The cell, shown in Fig. 1, has an overall diameter of 101.6 mm, a moissanite anvil diameter of 9.00 mm, a culet size of 3 mm, and a spring steel gasket 0.5 mm thick with a hole diameter of 2.5 mm. A 2.3 mm diameter by 100 {micro}m thick sample of {delta}-phase Pu-2 at.% Ga is compressed at a rate of approximately 0.05 GPa/minute to {approx}1 GPa to induce the phase transformation to {alpha}{prime}. Optical microscopy of the recovered specimen reveals a very fine microstructure that appears to be single phase, although the resolution of this technique is insufficient to differentiate between single and multiple phases if the grain size is below approximately 1 {micro}m. X-ray diffraction, using a laboratory Cu K{sub {alpha}} source with wavelength of 1.542{angstrom}, shows the monoclinic reflections from the {alpha}{prime} phase, strong peaks from the aluminum specimen holder, and weak peaks from the face-centered cubic {delta} phase as shown in Fig. 2. The recovered specimen is prepared for TEM and electron diffraction studies as described in Moore et al. [6]. TEM reveals small regions of {delta} phase with a very high dislocation density interspersed between the 10-100's nm {alpha}{prime} grains as shown in Fig. 3. Electron diffraction, shown in the insert in Fig. 3, clearly reveals the presence of the {delta} phase. This microstructure is in contrast to the {alpha}{prime} particles that form as a result of the low-temperature isothermal martensite in which the {alpha}{prime} particles are lath-shaped and significantly larger as shown in the optical micrograph in Fig. 4 of a sample cooled to -120 C and held for 10 hours. In these preliminary results, there is no evidence of either an amorphous phase, as suggested by Harbur [5], or the presence of a {gamma} phase. We expected to observe an amorphous phase based on the similarity of this experiment to that of Harbur [5]. It is possible that the {gamma} phase, as reported by Faure et al. [4], does form as an intermediate, but it is not retained to ambient pressure

Isothermal Martensitic and Pressure-Induced Delta to Alpha-Prime Phase Transformations in a Pu-Ga Alloy

A well-homogenized Pu-2 at.% Ga alloy can be retained in the metastable face-centered cubic {delta} phase at room temperature. Ultimately, this metastable {delta} phase will decompose via a eutectoid transformation to the thermodynamically stable monoclinic {alpha} phase and the intermetallic compound Pu{sub 3}Ga over a period of approximately 10,000 years [1]. In addition, these low solute-containing {delta}-phase Pu alloys are metastable with respect to an isothermal martensitic phase transformation to the {alpha}{prime} phase during low temperature excursions [2, 3] and are also metastable with respect to a {delta} {yields} {alpha}{prime} phase transformation with increases in pressure [3-5]. The low temperature {delta} {yields} {alpha}{prime} isothermal martensitic phase transformation in the Pu-2 at.% Ga alloy only goes to {approx}25% completion with the resultant {approx}20 {micro}m long by 2 {micro}m wide lath-shaped {alpha}{prime} particles dispersed within the {delta} matrix. In recently reported studies, Faure et al. [4] have observed a {delta} {yields} {gamma} {yields} {alpha}{prime} pressure-induced phase transformation sequence during a diamond anvil cell investigation and, based on x-ray diffraction and density and compressibility experiments, Harbur [5] has concluded that both {alpha}{prime} and an amorphous phase are present in samples that were pressurized and recovered. In this work, a large volume moissanite anvil cell is constructed to permit the pressurization and recovery of specimens of a size suitable for TEM and electron diffraction studies. The cell, shown in Fig. 1, has an overall diameter of 101.6 mm, a moissanite anvil diameter of 9.00 mm, a culet size of 3 mm, and a spring steel gasket 0.5 mm thick with a hole diameter of 2.5 mm. A 2.3 mm diameter by 100 {micro}m thick sample of {delta}-phase Pu-2 at.% Ga is compressed at a rate of approximately 0.05 GPa/minute to {approx}1 GPa to induce the phase transformation to {alpha}{prime}. Optical microscopy of the recovered specimen reveals a very fine microstructure that appears to be single phase, although the resolution of this technique is insufficient to differentiate between single and multiple phases if the grain size is below approximately 1 {micro}m. X-ray diffraction, using a laboratory Cu K{sub {alpha}} source with wavelength of 1.542{angstrom}, shows the monoclinic reflections from the {alpha}{prime} phase, strong peaks from the aluminum specimen holder, and weak peaks from the face-centered cubic {delta} phase as shown in Fig. 2. The recovered specimen is prepared for TEM and electron diffraction studies as described in Moore et al. [6]. TEM reveals small regions of {delta} phase with a very high dislocation density interspersed between the 10-100's nm {alpha}{prime} grains as shown in Fig. 3. Electron diffraction, shown in the insert in Fig. 3, clearly reveals the presence of the {delta} phase. This microstructure is in contrast to the {alpha}{prime} particles that form as a result of the low-temperature isothermal martensite in which the {alpha}{prime} particles are lath-shaped and significantly larger as shown in the optical micrograph in Fig. 4 of a sample cooled to -120 C and held for 10 hours. In these preliminary results, there is no evidence of either an amorphous phase, as suggested by Harbur [5], or the presence of a {gamma} phase. We expected to observe an amorphous phase based on the similarity of this experiment to that of Harbur [5]. It is possible that the {gamma} phase, as reported by Faure et al. [4], does form as an intermediate, but it is not retained to ambient pressure

Nucleation and growth of the Alpha-Prime Phase martensitic phase in Pu-Ga Alloys

In a Pu-2.0 at% Ga alloy, it is observed experimentally that the amount of the martensitic alpha-prime product formed upon cooling the metastable delta phase below the martensite burst temperature (M{sub b}) is a function of the holding temperature and holding time of a prior conditioning (''annealing'') treatment. Before subjecting a sample to a cooling and heating cycle to form and revert the alpha-prime phase, it was first homogenized for 8 hours at 375 C to remove any microstructural memory of prior transformations. Subsequently, conditioning was carried out in a differential scanning calorimeter apparatus at temperatures in the range between -50 C and 370 C for periods of up to 70 hours to determine the holding time and temperature that produced the largest volume fraction of alpha-prime upon subsequent cooling. Using transformation peak areas (i.e., the heats of transformation) as a measure of the amount of alpha-prime formed, the largest amount of alpha-prime was obtained following holding at 25 C for at prime least 6 hours. Additional time at 25 C, up to 70 hours, did not increase the amount of subsequent alpha-prime formation. At 25 C, the Pu-2.0 at% Ga alloy is below the eutectoid transformation temperature in the phase diagram and the expected equilibrium phases are {alpha} and Pu{sub 3}Ga, although a complete eutectoid decomposition of delta to these phases is expected to be extremely slow. It is proposed here that the influence of the conditioning treatment can be attributed to the activation of alpha-phase embryos in the matrix as a beginning step toward the eutectoid decomposition, and we discuss the effects of spontaneous self-irradiation accompanying the Pu radioactive decay on the activation process. Subsequently, upon cooling, certain embryos appear to be active as sites for the burst growth of martensitic alpha-prime particles, and their amount, distribution, and potency appear to contribute to the total amount of martensitic product formed. A modeling approach based on classical nucleation theory is presented to describe the formation of alpha-phase embryos during conditioning. The reasons why the holding times during conditioning become eventually ineffective in promoting more alpha-prime formation on cooling are discussed in terms of the differences in the potency of the embryos created in the delta matrix during conditioning and in terms of growth-impeding volume strains in the matrix resulting from an increasing number of martensite particles, thus opposing further growth. It is suggested that the disparate amounts of the alpha-prime formation reported in the literature following various studies may be in part a consequence of the fact that conditioning times at ambient temperatures are inevitably involved in any handling of radioactive samples prior to testing