Awareness and Localization of Explosives-Related Threats

Year Two Annual Report

F1-B: Nanomaterials for enhanced detection of explosives and mitigation of explosive events
Abstract This research is focused on the synthesis of nanomaterials which can be either incorporated in or used as high explosives. Alternative applications depending on the materials composition include incorporation in composites to either increase the resistance to blast or for enhanced detection post blast. The focus of year one has been to synthesize high surface area, low density, high Z number nanomaterials which have enhanced x-ray absorption for traditional detection. In addition by using semiconductor nanoparticles we are able to integrate novel and tunable optical properties into a energetic composite materials. To this end composite aerogel materials which are primarily composed of cadmium sulfide nanoparticles coated with gold have been successfully prepared, these aerogels are unique in that they are the first to incorporate the novel surface plasmon properties of the gold particles with the quantum confined optical effects of the cadmium sulfide nanoparticles.

I.

PARTICIPANTS
Name Title Faculty/Staff Institution
Texas Tech University Texas Tech University

Louisa Hope-Weeks Brandon Weeks

Associate Professor Associate Professor

Email

Phone
806-742-4487 806-742-3998

louisa.hope-weeks@ttu.edu brandon.weeks@ttu.edu

Name
Simerjeet Gill Preston Brown

PhD PhD

Degree Pursued

Students Institution
Texas Tech University Texas Tech University

Email
Simerjeet.gill@ttu.edu Preston.brown@ttu.edu

2010

Intended Year of Graduation

II.

PROJECT OVERVIEW AND SIGNIFICANCE

This work looks to exploit nanomaterials that have novel optical, electronic, and magnetic properties which can be incorporated into the high explosive. These materials, have two important functions: [1] They will act as pre-blast detection taggants. For this reason we will synthesize nanometer sized semiconductor nanocrystals (quantum dots) and magnetic particles containing transition metals. The added nanocrystals will provide alternate methods for detection. Another advantage is that the transition metal will enhance the x-ray absorption, which is a standard detection method in buildings and airports. [2] As a post-blast detection agent, they will provide a visual selection criteria for debris. The surface chemistry of both the semiconductor and magnetic nanocrystals can be modified by coating nanocrystals with an inert silica/ siloxane polymer. This basic chemistry can be expanded to include a diverse range of functionalities which can be achieved by chemically modifying polymer coatings that have reactive carboxyl surface groups.[3] This provides a means to further functionalize the surface with proteins (biotin or streptavidin) that allows for conjugation to biomolecules. By modifying the surface chemistry of the nanoparticles we will be able to ensure a homogenous composition of the final high explosive composite material. Another method to increase the survivability and detection of nanomaterials in an explosive blast is to use a complex matrix. The most promising matrix is a high surface area aerogel. The high porosity of the aerogel opens a number of avenues for both detection and forensics: (1) the aerogel matrix can be used to introduce high Z material that will increase detection probability by increasing the x-ray cross56

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Awareness and Localization of Explosives-Related Threats

section. (2) This high Z material could also be fluorescent, providing a screening method for forensic sample collection. (3) the aerogel matrix can be used to introduce a magnetic material which can aid in debris selection and collection (4) the pores of the aerogel could contain odorants (possibly polyamines) (5) the aerogel matrix can be modified to covalently incorporate energetic moieties allowing precise control of the composite material composition and density (6) The high-insulating capacity of the aerogel will protect materials incorporated into the against high temperature gradients. These materials are likely to be better as composite fillers since they can be self supporting monoliths. They also have mechanical properties which may enhance blast resistance. An alternative approach form enhanced structured composite energetic materials is to incorporate them into the oxidizer and fuel into a single homogenous matrix. To this end resorcinol and formaldehyde have been widely documented as a method to make carbon aerogels. This work has been limited by the inability to alter the chemistry by changing the alcohol functionality on the aromatic ring. Recently the utility of organic aerogels has successfully expanded to include gels which have greater functionality by substituting the resorcinol with an alterative 1,3 functionalized benzene derivatives. By substituting the alcohol with a more versatile and amendable functional group allows further modification of the gel either post- or pre-gelation. For example by substituting with benzene 1,3-diamine incorporates amine functionality which allows specific covalent attachment of any desired functionality (taggant or energetic material) throughout the gel. This careful control to the reaction chemistry ultimately controls the final composition of the composite materials. Alternatively substitutions of one or both the amine functionalities pre-gelation to incorporate the desired functionality will ultimately allow high surface area energetic materials with nanoscale dimensions to be formed with a the taggant and energetic material uniformly distributed throughout the composite.

III.
A.

RESEARCH AND EDUCATION ACTIVITY

State-of-the-Art and Technical Approach

Metal-semiconductor nanoparticles are of current interest due to the unique properties that can be exhibited due to the coupling of semiconductor excitons with the plasmon resonance of the metal at the interface.[4-6] The observed properties are highly dependent on the nature and alignment of the semiconductor and metal components. The ability to induce and tune the properties exhibited, especially for semiconducting components opens up tremendous scope for potential applications especially in the area of sensing. Alternatively sol-gel chemistry provides a straightforward route to assemble semiconductor nanoparticles into porous three-dimensional nanostructures with direct contact between the nanoparticle building blocks. In addition, an open accessible porous network is introduced which could expand the utility of the nanoparticles further. The sol-gel technique for assembling nanoparticles was first developed by Gacoin and cowokers for CdS nanoparticles, and is called nanoparticle condensation strategy.[7-9] In this strategy, the semiconductor nanoparticles are first prepared using a size selective synthesis. This can be either a room temperature synthesis involving arrested precipitation reactions conducted in water-in-oil microemulsions [10, 11] or a high-temperature synthesis using coordinating solvents.[12] The semiconductor nanoparticles are then surface capped with thiol which is followed by induced precipitation. The nanoparticles are them suspended in a suitable solvent and then treated with an oxidant which results in controlled aggregation of nanoparticles and finally formation of the gel network. The main advantage of the nanoparticle condensation strategy is that it allows greater control over resultant gel morphology due to the separation of the gel formation from the nanoparticle synthesis. In the present work, we describe the ability to adapt this novel approach to synthesize of aerogel networks comprised gold modified cadmium sulfide (CdS-Au) nanoparticles. This work is building upon on our initial findings in which the properties of the CdS-Ag aerogels were investigated.[13] We observed
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Awareness and Localization of Explosives-Related Threats

Year Two Annual Report

that the properties of the single nanoparticles were retained in the final aerogel. However the presence of the Ag dramatically affected the morphological structure of the CdS-Ag aerogels. Thus, we have expanded this investigation to develop a series of CdS-Au aerogels with varying gold concentration to determine whether metal concentration can be used to modify the resultant metal-semiconductor aerogel structure. Also, our aim was to access the scope of nanoparticle condensation strategy as a synthetic method to construct robust aerogel networks of metal modified semiconductor nanoparticles. By doing this we are able to determin the upper limit for Au incorportation, which ultimatly increases the average overall Z-number of the material. Gaining an understanding of the mechanism involved in metal-semiconductor gel formation, will allow us to futher control the overal density of the final materials which will of significant importance when forming the final energetic material composite.

B.

Major Contributions

The gelation of CdS-Au sols is achieved by addition of hydrogen peroxide as oxidant, which results in the removal of thiolate capping groups on the CdS-Au nanoparticle surface. The reactive sites are produced on the CdS-Au nanoparticle surface which leads to inter-particle interactions resulting in gel formation. In previous studies, it has been reported that the molar ratio of hydrogen peroxide to thiol used for gel formation dramatically impacts the transformation of colloidal sol to a stable gel.[7-9] The lower molar ratios lead to unstable gels and higher ratios result in significant syneresis which is followed by precipitation at even higher ratios. In present work, to investigate the role of oxidant in case of CdSAu system the molar ratio of hydrogen peroxide to thiol was varied from 4 to 50. Figure 1 represents schematic evolution of CdS-Au colloidal sol as a function of X, where X is the molar ratio of hydrogen peroxide to thiol, added to the reaction mixture. It was observed for X below 4 a translucent CdS-Au sol was formed and no significant gel formation was observed. This may be attributed to slow and insufficient oxidation of the thiol capping groups from the CdS-Au surface, which limits reactive sites for inter-particle interaction. With further increase in X, the degree of oxidation increases which destabilizes the CdS-Au sol and is accompanied by increase in aggregation of CdS-Au nanoparticles. The increased aggregation leads to gel formation when X is kept in the range 10-13 and robust CdS-Au gels were formed. However, upon close visual inspection small differences in the degree of syneresis is evident with X being more than 13. When X is 18 or higher syneresis of the gels was observed. This can be attributed to the expulsion of the solvent from the Figure 1: Schematic representation demonstrating pores as a consequence of a dominant oxidation the evolution of CdS-Au colloids at various X values, process. The degree of syneresis becomes more where X is the molar ratio of hydrogen peroxide to evident due to faster rate of gelation with an increasing 4-flourothiophenol and increases from 4 to 50 from left to right. value of X. Finally, at very high amounts of oxidant (X = 50) no gelation is observed, and the CdS-Au nanoparticles only precipitate. At this stage, very fast oxidation occurs yielding a lot of reactive sites together causing CdS-Au nanoparticles to precipitate out from the sol. The yellow-brown wet gels were transformed into aerogels (Figure A1.2-2) by exchanging the solvent with acetone followed by low temperature supercritical drying. The amount of gold added to CdS sol solution caused significant differences in the stability of the aerogel formed. The CdS-Au samples with lower gold concentration formed successful alcogels. However, upon supercritical drying significant
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shrinkage was observed and the aerogels formed were fragile and difficult to handle. This gel instability may be attributed to the fact that surface coverage of CdS nanoparticles by gold is not enough at these concentrations and surface is dominated by CdS-thiol bonds. The higher amount of hydrogen peroxide added for metal-semiconductor system leads to faster oxidation and weak CdS-Au alcogels which collapse during the drying process. The TEM micrographs clearly show the CdS-Au building blocks and the porous morphology of the CdSAu aerogels (Figure 2). The CdS-Au nanoparticles formed for all samples were between 5-15 nm in size. The TEM analyses also showed distinct dark electron dense areas which are the gold nanoparticles. These are clearly dispersed within a CdS nanoparticle matrix composed of spherical CdS nanoparticles. It is probable that the gold nanoparticles are attached to the sulfurrich defect sites on the surface of CdS nanoparticles.[14, 15] The negative charge from the dangling sulfur bonds, attracts the positively charged Au ions, and the high Au-S bond enthalpy (418 kJ/mole) [16] promotes the deposition and subsequent growth of Au at these sites.[14] The porous network of the lowest gold concentration aerogel showed distinct regions with confined CdS-Au nanoparticles. The particles were not clustered together and there were regions which were very thinly populated with CdS-Au nanoparticles. Increasing the gold concentration reveals the CdS-Au nanoparticles were spread evenly throughout the aerogel network. It was clearly observed CdSAu nanoparticles were joined together to form a well connected network. In case of the aerogel with highest gold concentration, the CdS-Au nanoparticles were separated from each other and no linking was observed in porous powder. In general, the successful monolithic aerogels showed similar porous pearl necklace morphology with well connected CdS-Au nanoparticles. The gold concentrations which formed either precipitates of weakly connected gels show reduced porosity with non-uniform distribution of weakly linked CdS-Au nanoparticles. This is in agreement with the fragile nature of Figure 2: TEM micrographs of aerogel of gold CdS-Au gel networks obtained using high and low gold coated cadmium sulfide nanoparticles where A concentrations. to D demonstrate the effect of increasing gold
concentration.

IV.

FUTURE PLANS

In the second year of this studying we will undertake specific tasks. 1. Synthesize metal oxides and sulfides with a high Z-number determine factors that effects structure and density 2. Evaluate the utility of metal oxides aerogels as composite fillers for energetic materials- determining stability-property-density relationships. 3. Evaluate the utility of metal sulfides as taggents for tradition energetic materials- determine survivability and detection limits 4. Synthesis of covalent organic aerogel-energetic nanocomposites-materials characterization and stability evaluation including drop hammer tests.

V.

LEVERAGING OF RESOURCES

This was a new start in 2009. We are submitting proposals enabled by this work to other agencies. Currently, a proposal in under review by the DoE to investigate high surface area aerogels as potential
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Awareness and Localization of Explosives-Related Threats

Year Two Annual Report

catalysts. We anticipate the additional proposals will be submitted to the NSF, Welch Foundation and ACS-PRF in 2010.

VI.
A.

DOCUMENTATION
Publications

S. Gill, P. Brown and LJ. Hope-Weeks Gold modified cadmium sulfide aerogels Journal of Sol-gel Science and Technology, submitted 2010

B. C.

Technology Transfer Seminars, Workshops and Short Courses

none to date

none to date

VII.
[1] [2] [3]

REFERENCES
T. Trindade, P. OBrien, and N. L. Pickett, Chemistry of Materials, 2001, 13, 3848-3858. Y. Wang and N. Herron, Journal of Physical Chemistry, 1991, 95, 525-532. M. Bruchez, M. Moronne, P. Gin, S. Weiss, and A. P. Alivisatos, Science, 1998, 281, 2013-2015.

[4] A. K. Pradhan, R. B. Konda, H. Mustafa, R. Mundle, O. Bamiduro, U. N. Roy, Y. Cui and A. Burger, Optics Express, 2008, 16, 6202-6208. [5] [6] W. T. Chen, T. T. Yang and Y. J. Hsu, Chemistry of Materials, 2008, 20, 7204-7206. R. de Paiva and R. Di Felice, Acs Nano, 2008, 2, 2225-2236.

[7] T. Gacoin, K. Lahlil, P. Larregaray and J. P. Boilot, Journal of Physical Chemistry B, 2001, 105, 10228-10235. [8] [9] [10] [11] [12] [13] [14] T. Gacoin, L. Malier and J. P. Boilot, Journal of Materials Chemistry, 1997, 7, 859-860. T. Gacoin, L. Malier and J. P. Boilot, Chemistry of Materials, 1997, 9, 1502-1506. C. Petit and M. P. Pileni, Journal of Physical Chemistry, 1988, 92, 2282-2286. L. Motte, F. Billoudet and M. P. Pileni, Journal of Physical Chemistry, 1995, 99, 16425-16429. Z. A. Peng and X. G. Peng, Journal of the American Chemical Society, 2001, 123, 183-184. S. K. Gill and L. J. Hope-Weeks, Chemical Communications, 2009, 4384-4386. A. E. Saunders, I. Popov and U. Banin, Journal of Physical Chemistry B, 2006, 110, 25421-25429.

[15] F. Rocco, A. K. Jain, M. Treguer, T. Cardinal, S. Yotte, P. Le Coustumer, C. Y. Lee, S. H. Park and J. G. Choi, Chemical Physics Letters, 2004, 394, 324-328. [16] D. R Lide,. CRC Handbook of Chemistry and Physics, 81st ed.;CRC Press: Boca Raton, FL, 2000.

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