Kinetics of the γ-δ phase transition in energetic nitramine-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine.

The solid, secondary explosive nitramine-octahydro-1,3,5,7-tetranitro-1,3,5,7 or HMX has four different stable polymorphs which have different molecular conformations, crystalline structures, and densities, making structural phase transitions between these nontrivial. Previous studies of the kinetics of the ß-δ HMX structural transition found this to happen by a nucleation and growth mechanism, where growth was governed by the heat of fusion, or melting, even though the phase transition temperature is more than 100 K below the melting point. A theory known as virtual melting could easily justify this since the large volume difference in the two phases creates a strain at their interface that can lower the melting point to the phase transition temperature through a relaxation of the elastic energy. To learn more about structural phase transitions in organic crystalline solids and virtual melting, here we use time-resolved X-ray diffraction to study another structural phase transition in HMX, γ-δ. Again, second order kinetics are observed which fit to the same nucleation and growth model associated with growth by melting even though the volume change in this transition is too small to lower the melting point by interfacial strain. To account for this, we present a more general model illustrating that melting over a very thin layer at the interface between the two phases reduces the total interfacial energy and is therefore thermodynamically favorable and can drive the structural phase transition in the absence of large volume changes. Our work supports the idea that virtual melting may be a more generally applicable mechanism for structural phase transitions in organic crystalline solids.

X-ray transmission movies of spontaneous dynamic events.

We describe a new x-ray radiographic imaging system which allows for continuous x-ray transmission imaging of spontaneous dynamic events. We demonstrate this method on thermal explosions in three plastic bonded formulations of the energetic material octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine. We describe the x-ray imaging system and triggering developed to enable the continuous imaging of a thermal explosion.

Intercomparison of calorimetry, Raman spectroscopy, and second harmonic generation applied to solid-solid phase transitions.

This paper compares several different observables for use in measuring the kinetics of solid-solid phase transitions. Relative advantages and disadvantages for each technique are described, and a direct comparison of results is made for the beta to delta polymorphic phase transition of the energetic nitramine, octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine.

Direct observation of the phenomenology of a solid thermal explosion using time-resolved proton radiography.

We present a new phenomenology for burn propagation inside a thermal explosion based on dynamic radiography. Radiographic images were obtained of an aluminum cased solid cylindrical sample of a plastic bonded formulation of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine. The phenomenology observed is ignition followed by cracking in the solid accompanied by the propagation of a radially symmetric front of increasing proton transmission. This is followed by a further increase in transmission through the sample, ending after approximately 100 micros. We show that these processes are consistent with the propagation of a convective burn front followed by consumption of the remaining solid by conductive particle burning.

Analysis of the detective quantum efficiency of a developmental detector for digital mammography.

We are developing a modular detector for applications in full field digital mammography and for diagnostic breast imaging. The detector is based on a design that has been refined over the past decade for applications in x-ray crystallography [Kalata et al., Proc. SPIE 1345, 270-279 (1990); Phillips et al. ibid. 2009, 133-138 (1993), Phillips et al., Nucl. Instrum. Methods Phys. Rev. A 334, 621-630 (1993)]. The full field mammographic detector, currently undergoing clinical evaluation, is formed from a 19 cm x 28 cm phosphor screen, read out by a 2 x 3 array of butted charge-coupled device (CCD) modules. Each 2k x 2k CCD is optically coupled to the phosphor via a fiber optic taper with dimensions of 9.4 cm x 9.4cm at the phosphor. This paper describes the imaging performance of a two-module prototype, built using a similar design. In this paper we use cascaded linear systems analysis to develop a model for calculating the spatial frequency dependent noise power spectrum (NPS) and detective quantum efficiency (DQE) of the detector using the measured modulation transfer function (MTF). We compare results of the calculation with the measured NPS and DQE of the prototype. Calculated and measured DQEs are compared over a range of clinically relevant x-ray exposures and kVps. We find that for x-ray photon energies between 10 and 28 keV, the detector gain ranges between 2.5 and 3.7 CCD electrons per incident x-ray, or approximately 5-8 electrons per absorbed x ray. Using a Mo/Mo beam and acrylic phantom, over a detector entrance exposure range of approximately 10 to 80 mR, the volume under the measured 2-d NPS of the prototype detector is proportional to the x-ray exposure, indicating quantum limited performance. Substantial agreement between the calculated and measured values was obtained for the frequency and exposure dependent NPS and DQE over a range of tube voltage from 25 to 30 kVp.

Conformational changes in the core structure of bacteriorhodopsin.

Bacteriorhodopsin (bR) is the light-driven proton pump found in the purple membrane of Halobacterium salinarium. In this work, structural changes occurring during the bR photocycle in the core structure of bR, which is normally inaccessible to hydrogen/deuterium (H/D) exchange, have been probed. FTIR difference bands due to vibrations of peptide groups in the core region of bR have been assigned by reconstituting and regenerating delipidated bR in the presence of D2O. Exposure of bR to D2O even after long periods causes only a partial shift of the amide II band due to peptide NH --> ND exchange only of peripheral peptide structure. However, the amide II band completely downshifts when reconstitution/regeneration of bR is performed in the presence of D2O, indicating that almost the entire core backbone structure of bR undergoes H/D exchange. Peripheral regions can then be reexchanged in H2O, leaving the core backbone region deuterated. Low-temperature FTIR difference spectra on these core-deuterated samples reveal that peptide groups in the core region respond to retinal isomerization as early as the K intermediate. By formation of the M intermediate, infrared differences in the amide I region are dominated by much larger structural changes occurring in the core structure. In the amide II region, difference bands appear upon K formation and increase upon M formation which are similar to those observed upon the cooling of bacteriorhodopsin. This work shows that retinal isomerization induces conformational changes in the bacteriorhodopsin core structure during the early photocycle which may involve an increase in the strength of intramolecular alpha-helical hydrogen bonds.

Enhanced optical limiting in derivatized fullerenes.

We have observed enhanced optical limiting behavior in solutions of a derivatized fullerene (phenyl-C(61)-butyric acid cholesteryl ester) from 532 to 700 nm. Transient absorption measurements determined the spectral and temporal regions of interest for optical limiting in C(60) and in C(60) derivatives that are due to a reverse saturable absorption mechanism and predicted enhanced limiting at longer wavelengths. Intensity-dependent transmission measurements made at several wavelengths confirmed these results. The increased solubility and the broadened ground-state absorption of the functionalized C(60) make it suitable for use as an optical limiter in the red and the near infrared.

Photoinduced electron transfer from a conducting polymer to buckminsterfullerene.

Evidence for photoinduced electron transfer from the excited state of a conducting polymer onto buckminsterfullerene, C(60), is reported. After photo-excitation of the conjugated polymer with light of energy greater than the pi-pi* gap, an electron transfer to the C(60) molecule is initiated. Photoinduced optical absorption studies demonstrate a different excitation spectrum for the composite as compared to the separate components, consistent with photo-excited charge transfer. A photoinduced electron spin resonance signal exhibits signatures of both the conducting polymer cation and the C(60) anion. Because the photoluminescence in the conducting polymer is quenched by interaction with C(60), the data imply that charge transfer from the excited state occurs on a picosecond time scale. The charge-separated state in composite films is metastable at low temperatures.