Rajen B. Patel

Nanoscale 2CL-20·HMX high explosive cocrystal synthesized by bead milling

Energetic nanoscale 2CL-20·HMX, a cocrystal of CL-20 and HMX in a 2 : 1 molar ratio, was prepared by a novel method of bead milling an aqueous suspension of e-CL-20 and β-HMX. The conversion of the coformers to the cocrystal form was monitored by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis of specimens sampled at various milling times. Complete conversion to the cocrystal form was achieved by 60 minutes of milling. Rounded 2CL-20·HMX cocrystal particles with a mean size below 200 nm were produced. A mechanism for the conversion of the coformers to the cocrystalline form is postulated based on the experimental results. As an inherently safe manufacturing method, the aqueous bead milling process has great potential in advancing cocrystal research and applications in the field of energetic materials.

Boron-Filled Hybrid Carbon Nanotubes

A unique nanoheterostructure, a boron-filled hybrid carbon nanotube (BHCNT), has been synthesized using a one-step chemical vapor deposition process. The BHCNTs can be considered to be a novel form of boron carbide consisting of boron doped, distorted multiwalled carbon nanotubes (MWCNTs) encapsulating boron nanowires. These MWCNTs were found to be insulating in spite of their graphitic layered outer structures. While conventional MWCNTs have great axial strength, they have weak radial compressive strength, and do not bond well to one another or to other materials. In contrast, BHCNTs are shown to be up to 31% stiffer and 233% stronger than conventional MWCNTs in radial compression and have excellent mechanical properties at elevated temperatures. The corrugated surface of BHCNTs enables them to bond easily to themselves and other materials, in contrast to carbon nanotubes (CNTs). BHCNTs can, therefore, be used to make nanocomposites, nanopaper sheets, and bundles that are stronger than those made with CNTs.

Dependence of Raman Spectral Intensity on Crystal Size in Organic Nano Energetics.

Raman spectra for various nitramine energetic compounds were investigated as a function of crystal size at the nanoscale regime. In the case of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20), there was a linear relationship between intensity of Raman spectra and crystal size. Notably, the Raman modes between 120 cm−1 and 220 cm−1 were especially affected, and at the smallest crystal size, were completely eliminated. The Raman spectral intensity of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), like that of CL-20s, depended linearly on crystal size. The Raman spectral intensity of 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), however, was not observably changed by crystal size. A non-nitramine explosive compound, 2,4,6-triamino-1,3,5- trinitrobenzene (TATB), was also investigated. Its spectral intensity was also found to correlate linearly with crystal size, although substantially less so than that of HMX and CL-20. To explain the observed trends, it is hypothesized that disordered molecular arrangement, originating from the crystal surface, may be responsible. In particular, it appears that the thickness of the disordered surface layer is dependent on molecular characteristics, including size and conformational flexibility. Furthermore, as the mean crystal size decreases, the volume fraction of disordered molecules within a specimen increases, consequently, weakening the Raman intensity. These results could have practical benefit for allowing the facile monitoring of crystal size during manufacturing. Finally, these findings could lead to deep insights into the general structure of the surface of crystals.

Evidence for Stable High-Temperature Ferromagnetism in Fluorine-Treated C60

It is shown by magnetic field dependent ac susceptibility, magnetic force microscopy, and ferromagnetic resonance that exposure of C60 to fluorine at 160°C produces a stable ferromagnetic material with a Curie temperature well above room temperature. The exposure to fluorine is accomplished by decomposing a fluorine-rich polymer, trifluorochloroethylene [F2C–CFCl]n, which has C60 imbedded in it. Based on previous experimental observations and molecular orbital calculations, it is suggested that the ferromagnetism is arising from crystals of C60–F.

Ferromagnetism in Thermally Decomposed Polyimide Films

Magnetic resonance studies of polyimide films thermally decomposed in flowing N2 at 520°C reveal the presence of two very different magnetic resonance spectra at room temperature. One spectra is a sharp temperature independent paramagnetic resonance line having a g value of 1.990, typical of a free radical. The other much broader line centered at lower field displays a marked broadening and shift to lower magnetic field as the temperature is lowered, characteristic of a ferromagnetic resonance (FMR) signal. Measurements of the AC susceptibility as a function of magnetic field strength confirm the existence of ferromagnetism at room temperature. Magnetic force microscope (MFM) imaging at room temperature show evidence of long thin ferromagnetic regions in the decomposed polymer.