Sublimation and Diffusion Kinetics of 2,4,6-Trinitrotoluene (TNT) Single Crystals by Atomic Force Microscopy (AFM).

In this article, we report the in-situ nanoscale experimental measurement of sublimation rates, activation energy of sublimation, and diffusion coefficients of 2,4,6-trinitrotoluene (TNT) single crystals in air using atomic force microscopy (AFM). The crystals were prepared by slow evaporation at 5 °C using acetone-dissolved TNT. The mass loss was calculated by monitoring the shrinkage of the surface area of layered islands formed on the surface of the TNT crystals due to sublimation upon isothermal heating at temperatures below the melting point. The results suggest the sublimation process occurs via two-dimensional detachment of TNT molecules from the non-prominent facets on the crystal surface which imitates the nucleation and crystal growth process. Sublimation rates are one order of magnitude smaller than previously reported values. However, the calculated activation energy (112.15 ± 3.2 kJ/mol) and temperature-dependent sublimation rates agree well with the reported values for TNT thin films and microcrystals determined by UV-vis absorbance spectroscopy and quartz crystal microscopy (QCM) (90-141 kJ/mol). The average diffusion coefficient is (4.35 × 10-6 m2/s) which is within the range of the reported theoretical values with an average of 5.59 × 10-6 m2/s, and about 25% less than that determined using thermogravimetric analysis for powder TNT.

Investigation of Size-Dependent Sublimation Kinetics of 2,4,6-Trinitrotoluene (TNT) Micro-Islands Using In Situ Atomic Force Microscopy.

Kinetic thermal analysis was conducted using in situ atomic force microscopy (AFM) at a temperature range of 15-25 °C to calculate the activation energy of the sublimation of 2,4,6-trinitrotoluene (TNT) islands. The decay of different diameter ranges (600-1600 nm) of TNT islands was imaged at various temperatures isothermally such that an activation energy could be obtained. The activation energy of the sublimation of TNT increases as the diameter of islands increases. It was found that the coarsening and the sublimation rate of TNT islands can be determined by the local environment of the TNT surface. This result demonstrates that a diffusion model cannot be simply applied to "real world" systems for explaining the sublimation behavior and for estimating the coarsening of TNT.

Non-Isothermal Sublimation Kinetics of 2,4,6-Trinitrotoluene (TNT) Nanofilms.

Non-isothermal sublimation kinetics of low-volatile materials is more favorable over isothermal data when time is a crucial factor to be considered, especially in the subject of detecting explosives. In this article, we report on the in-situ measurements of the sublimation activation energy for 2,4,6-trinitrotoluene (TNT) continuous nanofilms in air using rising-temperature UV-Vis absorbance spectroscopy at different heating rates. The TNT films were prepared by the spin coating deposition technique. For the first time, the most widely used procedure to determine sublimation rates using thermogravimetry analysis (TGA) and differential scanning calorimetry (DSC) was followed in this work using UV-Vis absorbance spectroscopy. The sublimation kinetics were analyzed using three well-established calculating techniques. The non-isothermal based activation energy values using the Ozawa, Flynn⁻Wall, and Kissinger models were 105.9 ± 1.4 kJ mol-1, 102.1 ± 2.7 kJ mol-1, and 105.8 ± 1.6 kJ mol-1, respectively. The calculated activation energy agreed well with our previously reported isothermally-measured value for TNT nanofilms using UV-Vis absorbance spectroscopy. The results show that the well-established non-isothermal analytical techniques can be successfully applied at a nanoscale to determine sublimation kinetics using absorbance spectroscopy.

Large-area preparation of high-quality and uniform three-dimensional graphene networks through thermal degradation of graphene oxide-nitrocellulose composites.

We demonstrate a simple method to prepare high-quality and uniform three-dimensional (3D) graphene networks through thermal degradation of graphene oxide (GO)-nitrocellulose composites over a large area. The nitrocellulose simultaneously acts as a support and aids in the reduction of GO by exothermic decomposition. The graphene networks have tunable porous morphology where the pore size can be controlled by adjusting the concentration of GO in the composite. This new technique is a very simple method to obtain 3D graphene networks and has the potential to produce 3D graphene-modified substrates for use in energy storage and conversion applications, in supporting frameworks of catalyst, and in sensors. In this report, the prepared 3D graphene networks were directly used as the electrodes of supercapacitors without using a binding agent and/or conducting additive with a high specific capacitance of 162.5 F g(-1) at 0.5 A g(-1) current density.

Polyethylenimine facilitated ethyl cellulose for hexavalent chromium removal with a wide pH range.

Ethyl cellulose (EC) composites modified with 20.0 wt % polyethylenimine (PEI) (PEI/ECs) demonstrated effective hexavalent chromium, [Cr(VI)], removal from solutions with a wide pH range. For example, 4.0 mg/L Cr(VI) solution with a pH below 3.0 was completely purified by 3.0 g/L PEI/ECs within 5 min, much faster than the as-received EC (2 h) and activated carbon (several hours). These PEI/ECs adsorbents has overcome the low pH limitation of Cr(VI) removal; for example, 4.0 mg/L Cr(VI) solution with a pH of 11.0 was completely purified within 15 min. These adsorbents followed chemical adsorption as revealed from the pseudo-second-order kinetic study. These PEI/ECs following the isotherm Langmuir model have a maximum adsorption capacity of 36.8 mg/g, much higher than pure EC (12 mg/g), tetrabutylammonium-modified celluloses (16.67 mg/g), and magnetic carbon (16 mg/g). The reduction of Cr(VI) to Cr(III) by the oxidation of amine groups and hydroxyl groups of PEI/ECs was verified as the main mechanism for the Cr(VI) removal.

Sublimation kinetics and diffusion coefficients of TNT, PETN, and RDX in air by thermogravimetry.

The diffusion coefficients of explosives are crucial in their trace detection and lifetime estimation. We report on the experimental values of diffusion coefficients of three of the most important explosives in both military and industry: TNT, PETN, and RDX. Thermogravimetric analysis (TGA) was used to determine the sublimation rates of TNT, PETN, and RDX powders in the form of cylindrical billets. The TGA was calibrated using ferrocene as a standard material of well-characterized sublimation rates and vapor pressures to determine the vapor pressures of TNT, PETN, and RDX. The determined sublimation rates and vapor pressures were used to indirectly determine the diffusion coefficients of TNT, PETN, and RDX for the first time. A linear log-log dependence of the diffusion coefficients on temperature is observed for the three materials. The diffusion coefficients of TNT, PETN, and RDX at 273 K were determined to be 5.76×10(-6)m(2)/sec, 4.94×10(-6)m(2)/s, and 5.89×10(-6)m(2)/s, respectively. Values are in excellent agreement with the theoretical values in literature.

Preparation of sub-micron nitrocellulose particles for improved combustion behavior.

A novel method to prepare sub-micron nitrocellulose particles with spherical shape is demonstrated. The morphology of the nitrocellulose can be controlled by the solvent and the growth temperature. Using dimethylformamide (DMF) at a growth temperature is 5°C, reproducibly yielded spherical nitrocellulose particles. The final diameter of the prepared nitrocellulose particles can be further tuned by concentration. The smallest particles in this study were found to have diameters of 500nm at a concentration of 5-10mg/ml with 2 micron spheres formed at 30mg/ml. Furthermore, the thermal properties and the burn rates of the prepared materials are studied by differential scanning calorimetry and digital high-speed photography, respectively. In comparison to the bulk nitrocellulose material, the sub-micron nitrocellulose particles have lower decomposition activation energy, a 350% increase in burn rate, and a more complete combustion.

Tip induced crystallization lithography.

We demonstrate a new technique for efficiently fabricating large-area organic crystal arrays on substrates using tip induced crystallization lithography (TICL). This technique depends on coating an amorphous organic thin film on a substrate and then inducing crystallization of the thin film using an atomic force microscope tip. After the noncrystalline materials are removed from the substrate by heating or washing, the organic crystal arrays are stable on the substrate. In this communication, the size of the smallest feature made using TICL technique is less than 1 µm.

Effect of humidity and hydrophobicity on the tribological properties of self-assembled monolayers.

The tribological properties of two distinctive alkanethiol SAMs, 16-mercaptohexadecanoic acid (MHA) and 1-octadecanethiol (ODT), on gold substrates in various humidity conditions were examined by lateral force microscopy (LFM). The results suggest that hydrophobic ODT SAM is insensitive to humidity. The difference of lateral force signal is within ±10% regardless of humidity. The lateral force signal of hydrophilic MHA SAMs has a significant decrease in signal in humid environments. The influence of bulk water was also investigated by LFM. By imaging under water, the capillary force is eliminated on ODT SAMs, which leads to a lower lateral force. However, the lateral force image was reversed on MHA SAMs, which suggested that hydrophobic forces dominated in water.

In situ direct measurement of vapor pressures and thermodynamic parameters of volatile organic materials in the vapor phase: benzoic acid, ferrocene, and naphthalene.

We report the direct determination of vapor pressures and optical and thermodynamic parameters of powders of low-volatile materials in their vapor phase using a commercial UV/Vis spectrometer. This methodology is based on the linear proportionality between the density of the saturated gas of the material and the absorbance of the gas at different temperatures. The vapor pressure values determined for benzoic acid and ferrocene are in good agreement with those reported in the literature with ∼2-7 % uncertainty. Thermodynamic parameters of benzoic acid, ferrocene, and naphthalene are determined in situ at temperatures below their melting points. The sublimation enthalpies of the investigated organic molecules are in excellent agreement with the ICTAC recommended values (less than 1 % difference). This method has been used to measure vapor pressures and thermodynamic parameters of organic volatile materials with vapor pressures of ∼0.5-355 Pa in the 50-100 °C temperature range.

Metal-organic frameworks (MOFs) as safer, structurally reinforced energetics.

Second-generation cobalt and zinc coordination architectures were obtained through efforts to stabilize extremely sensitive and energetic transition-metal hydrazine perchlorate ionic polymers. Partial ligand substitution by the tridentate hydrazinecarboxylate anion afforded polymeric 2D-sheet structures never before observed for energetic materials. Carefully balanced reaction conditions allowed the retention of the noncoordinating perchlorate anion in the presence of a strongly chelating hydrazinecarboxylate ligand. High-quality X-ray single-crystal structure determination revealed that the metal coordination preferences lead to different structural motifs and energetic properties, despite the nearly isoformulaic nature of the two compounds. Energetic tests indicate highly decreased sensitivity and DFT calculations suggest a high explosive performance for these remarkable structures.

Aerobic Oxidation of 9H-Fluorenes to 9-Fluorenones using Mono-/Multilayer Graphene-Supported Alkaline Catalyst.

The synthesis of 9-fluorenone derivatives has been achieved in high yield and with high purity by aerobic oxidation of 9H-fluorenes at room temperature in the presence of a graphene-supported KOH composite that acts as a catalyst in N,N-dimethylformamide. The new protocol involves very simple work-up procedures, and the solvent and the catalyst can be recycled and reused. A scaled-up preparative study employing this method was also conducted and showed its advantages of being both cost-effective and environmentally friendly, and has potential for application in industrial processes.

Embossing of organic thin films using a surfactant assisted lift-off technique.

A simple technique for patterning organic materials using a surfactant assisted lift-off method is proposed. Thin films of various organic materials are prepared, and areas in contact with a surfactant coated poly(dimethylsiloxane) (PDMS) stamp are selectively removed. The general applicability of this technique is shown for materials containing nitrate, amine, and carboxylic acid functional groups. This technique provides a new methodology for fabricating patterns with vertical dimensions ranging from 30 nm up to 3 µm on organic thin films with specific functional groups.

Rapid estimation of thermodynamic parameters and vapor pressures of volatile materials at nanoscale.

Non-isothermal measurements of thermodynamic parameters and vapor pressures of low-volatile materials are favored when time is a crucial factor to be considered, such as in the case of detection of hazardous materials. In this article, we demonstrate that optical absorbance spectroscopy can be used non-isothermally to estimate the thermodynamic properties and vapor pressures of volatile materials with good accuracy. This is the first method to determine such parameters in nanoscale in just minutes. Trinitrotoluene (TNT) is chosen because of its low melting temperature, which makes it impossible to determine its thermodynamic parameter by other rising-temperature techniques, such as thermogravimetric analysis (TGA). The well-characterized vapor pressure of benzoic acid is used to calibrate the spectrometer in order to determine the vapor pressure of low-volatile TNT. The estimated thermodynamic properties of both benzoic acid and TNT are in excellent agreement with the literature. The estimated vapor pressure of TNT is one order of magnitude larger than that determined isothermally using the same method. However, the values are still within the range reported in the literature. The data indicate the high potential for use of rising-temperature absorbance spectroscopy in determining vapor pressures of materials at nanometer scale in minutes instead of hours or days.

Ionic polymers as a new structural motif for high-energy-density materials.

Energetic materials have been used for nearly two centuries in military affairs and to cut labor costs and expedite laborious processes in mining, tunneling, construction, demolition, and agriculture, making a tremendous contribution to the world economy. Yet there has been little advancement in the development of altogether new energetic motifs despite long-standing research efforts to develop superior materials. We report the discovery of new energetic compounds of exceptionally high energy content and novel polymeric structure which avoid the use of lead and mercury salts common in conventional primary explosives. Laboratory tests indicate the remarkable performance of these Ni- and Co-based energetic materials, while DFT calculations indicate that these are possibly the most powerful metal-based energetic materials known to date, with heats of detonation comparable with those of the most powerful organic-based high explosives currently in use.

Measuring the activation energy of thiol desorption using lateral force microscopy.

Thermal stability of self-assembled monolayers (SAMs) is important for applications in various surface science applications. As a model material, 16-mercaptohexadecanoic acid (MHA) on template stripped gold surfaces was investigated to determine the effect of temperature on the change of lateral force signal using atomic force microscopy (AFM). Friction force signals were obtained at various temperatures in order to determine whether it was possible to correlate the friction signal with desorption of the thiol molecule from the surface. Samples were heated for up to 10 h ranging from 40 to 80 °C in air and scanned every hour. A kinetic model was introduced to correlate the lateral force signal to the activation energy of desorption of the SAM from gold surface with heating. The activation energy of the detachment using this technique is 25.4 kcal/mol, which is consistent with other more complex techniques.

Thermo-optical determination of vapor pressures of TNT and RDX nanofilms.

Accurate thermodynamic parameters of thin films of explosives are important for understanding their behavior in the nanometer scale as well as in standoff detection. Using UV-absorbance spectroscopy technique, accurate thermodynamic parameters such as activation energies of sublimation, sublimation rates, and vapor pressures of the explosives cyclotrimethylenetrinitramine (RDX) and 2,4,6-trinitrotoluene (TNT) were determined. The values of these parameters are in excellent agreement with those reported using traditional experiments based on gravimetry. In terms of the Clapeyron equation, the dependence of RDX and TNT vapor pressures on temperature can be described by the relations LnP (Pa)=39.6-15459/T (K) and LnP (Pa)=34.9-12058/T (K), respectively. Heats of sublimation of RDX and TNT were also determined to be 128kJ/mol and 100.2kJ/mol, respectively.

Simple method for determining the vapor pressure of materials using UV-absorbance spectroscopy.

Accurate thermodynamic parameters of thin films of materials are crucial in understanding their behavior in the nanometer scale. A new and simple method for determining the vapor pressure and thermodynamic properties of nanometer thick films of materials was developed based on UV-absorbance spectroscopy. Well-characterized benzoic acid was used to calibrate the spectrometer and the experimental conditions. The thermodynamic properties of pentaerythritol tetranitrate (PETN) were determined to validate the use of this new method. The estimated values of the thermodynamic parameters of PETN are in excellent agreement with the values reported using the most widely used Knudsen effusion method for determining vapor pressure lower than 1 pascal. The elegance of this method is its simplicity. The results indicate that UV-absorbance spectroscopy is a model-free and powerful technique in determining thermodynamic parameters in the nanoscale.

Effect of Zn doping on the sublimation rate of pentaerythritol tetranitrate using atomic force microscopy.

A series of Zn ion-doped pentaerythritol tetranitrate (PETN) nanoislands in the form of thin films were prepared on Si substrates using spin coating. The effect of Zn concentrations on the sublimation energy was investigated by atomic force microscopy (AFM). The pure and Zn-doped nanoislands are imaged by AFM in contact mode at room temperature after annealing isothermally for a given time. The volume of the islands starts to decrease after annealing at 45 degrees C for pure PETN, whereas Zn-doped nanoislands start to decrease in height and volume after annealing at 55-58 degrees C. The minimum activation energy is found to be 29.7 Kcal/mol for 1,000 ppm Zn concentration. These studies are important for the long-term stabilization of PETN.

Engineering the microstructure of organic energetic materials.

The initiation sensitivity is highly dependent on void structures within an energetic material. It is technically feasible to modify the initiation sensitivity by lithographically defining the size and distribution of included voids on the micro- and nanoscale. We proposed a method to pattern organic energetic materials using microcontact printing of self-assembled monolayers. Pentaerythritol tetranitrate is spin-coated from solution as films onto patterned self-assembled monolayers. Images are presented for arbitrary patterns created based on the surface chemistry and concentration of the energetic material.