The present invention relates to energetic materials and, in particular, to a method for the preparation of triaminotrinitrobenzene microparticles with controlled morphology.
Consistent and optimized sensitivity and energy density of energetic materials are essential to their performance and safety in applications such as explosives and propellants. These factors heavily rely on the microscopic morphology of energetic materials including crystalline size, shape, uniformity and purity. See M. Ghosh et al., Cryst. Growth Des. 14, 5053 (2014). Triaminotrinitrobenzene (TATB) is a powerful energetic material which displays superior insensitivity to elements such as shock, impact, vibration or fire over any other known energetic material. See S. F. Rice and R. L. Simpson, The Unusual Stability of TATB: A Review of the Scientific Literature, Lawrence Livermore National Laboratory, Livermore, Calif. (1990). This insensitivity makes TATB the best choice where absolute safety is required. See B. M. Dobratz, The Insensitive High Explosive Triaminotrinitrobenzene (TATB): Development and Characterization, Los Alamos Scientific Laboratory, Los Alamos, N M (1995); W. E. Voreck et al., U.S. Pat. No. 5,597,974 A (28 Jan. 1997); and R. Thorpe and W. R. Feairheller, Development of Processes for Reliable Detonator Grade Very Fine Secondary Explosive Powders, Monsanto Research Corporation, Miamisburg, Ohio (1988). However, TATB particles prepared by existing methods typically lack uniformity in crystalline morphology. Such irregularity limits the potential to produce TATB with reproducible and predictable performance. Further, the sharp edges of existing energetic material particles result in detonation hot spots which are responsible for reducing energetic material stability. See M. Ghosh et al., Cryst. Growth Des. 14, 5053 (2014).
Therefore, a need remains for TATB microparticles with uniform particle size and spherical shape.
The present invention is directed to an inexpensive and rapid synthesis for monodispersed TATB microparticles based on recrystallization of TATB within ionic liquid micelles. The method comprises providing a first solution comprising triaminotrinitrobenzene dissolved in an ionic liquid, such as 1-butyl-3-methylimidazolium; providing a second solution comprising a nonionic surfactant and a solvent that is immiscible in and has a high polarity contrast against the ionic liquid, such as octane; mixing the first and the second solutions while being sonicated to form an emulsion comprising micelles of the first solution dispersed in the solvent; and adding an anti-solvent precipitant to the emulsion to precipitate microparticles of triaminotrinitrobenzene in the micelles. The microparticles can then be separated from the micelles, for example by centrifugation. The choice of a surfactant with proper hydrophilic-lipophilic balance value is important to micelle formation and therefore successful microparticle production. Therefore, the nonionic surfactant can have hydrophilic-lipophilic balance (HLB) value between 3-8, such as sorbitan ester, ethoxylated sorbitan ester, or polyethylene glycol alkyl ether. Depending on recrystallization speed of TATB, different microparticle morphologies of either quasi-spherical or faceted can be obtained. For example, if the anti-solvent precipitant is water, quasi-spherical microparticles are formed. If the anti-solvent precipitant is an alcohol, faceted microparticles are formed. Due to their desirable size and morphology, these TATB microparticles show even greater insensitivity and improved reproducibility and reliability of explosive devices than currently available TATB products.
The detailed description will refer to the following drawings, wherein like elements are referred to by like numbers.
Efforts to achieve TATB products with uniform particle size and spherical shape have been reported. See D. W. Firsich et al., TATB Purification and Particle Size Modification: An Evaluation of Processing Options, Mound Laboratory, Miamisburg, O H (1990); G. Yang et al., Propellants Explos. Pyrotech. 31, 390 (2006); T. Y. Han et al., New J. Chem. 33, 50 (2009); M. Foltz et al., J. Mater. Sci. 31, 1893 (1996); M. B. Talawar et al., J. Hazard. Mater. 137, 1848 (2006); L. Yang et al., Chin. J. Chem. 30, 293 (2012); and X. Tan et al., Nano 8, 573 (2013). These methods are mainly based on variations of recrystallization of TATB from its solution in concentrated sulfuric acid or dimethyl sulfoxide. The resultant TATB particles display only limited yield and improvement on quality compared with raw material from industrial suppliers. Additionally, the use of concentrated sulfuric acid significantly increases the cost of equipment and imposes potential danger to operators.
The present invention is directed to a micelle-assisted synthesis of monodispersed TATB microparticles using an ionic solvent and a nonionic surfactant. As described above, the choice of the surfactant with proper HLB value is a key to successful microparticle production. Depending on recrystallization speed of TATB, different morphologies of either quasi-spherical or faceted microparticles can be obtained. Due to their desirable size and morphology, these TATB microparticles are expected to show even greater insensitivity and improved reproducibility and reliability of explosive devices than currently available TATB products.
An exemplary method to form TATB microparticles is illustrated in
As shown in
The product microparticles were examined by powder X-ray diffraction (XRD) measurements to confirm their composition. In
TATB produced by recrystallization methods have been reported that do not exhibit the monodispersity of microparticles of the present invention. See T. Y. Han et al., New J. Chem 33, 50 (2008); M. Foltz et al., J. Mater. Sci. 31, 1893 (1996); G. Yang et al., Propellants Explos. Pyrotech. 31, 390 (2006); and M. Foltz et al., J. Mater. Sci. 31, 1741 (1996). The significantly improved morphology and uniformity of the microparticles are attributed to the surfactant-driven micelle formation. To study the mechanism, a control experiment was conducted under the same conditions except for the absence of surfactant. In this case, large chunks of yellow agglomerates were produced upon addition of water. As can be seen in SEM image shown in
To obtain deeper insights into the role of the Span 80 surfactant and confirm the micelle confinement mechanism, the synthesis was repeated with another common ionic surfactant, SDS. As described above, the hydrophilic-lipophilic balance, or HLB, is a parameter widely used to evaluate and predict the performance of surfactants. See W. Griffin, J. Soc. Cosm. Chem. 1, 311 (1949); W. Griffin, J. Soc. Cosm. Chem. 5, 249 (1954); and J. Davies, A quantitative kinetic theory of emulsion type, I. Physical chemistry of the emulsifying agent, Proceedings of International Congress of Surface Activity, (1957), pp. 426. Surfactants with HLB ranging between about 3 and 8 are ideal emulsifiers for water-in-oil type micelles. Span 80 has a HLB of 4.3 and was predicted to encapsulate the highly polar ionic liquid in the continuous non-polar phase of octane. On the other hand, SDS with a much higher HLB value of 40 is favorable for oil-in-water type emulsions and was not expected to form micelles. As expected, the product shown in
In order to study the relationship between recrystallization speed and the morphology of the TATB microparticles, water was replaced by ethanol as the precipitant. Ethanol is miscible with both BMA and octane. Therefore, with the same injection rate, less precipitant would enter the BMA micelles causing a slower recrystallization process of TATB. As shown by
The present invention has been described as a method for preparation of TATB microparticles. It will be understood that the above description is merely illustrative of the applications of the principles of the present invention, the scope of which is to be determined by the claims viewed in light of the specification. Other variants and modifications of the invention will be apparent to those of skill in the art.
This application claims the benefit of U.S. Provisional Application No. 62/540,840, filed Aug. 3, 2017, and U.S. Provisional Application No. 62/656,716, filed Apr. 12, 2018, both of which are incorporated herein by reference.
This invention was made with Government support under Contract No. DE-NA0003525 awarded by the United States Department of Energy/National Nuclear Security Administration. The Government has certain rights in the invention.
Number | Date | Country | |
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62540840 | Aug 2017 | US | |
62656716 | Apr 2018 | US |