Name: preparation and reactivity of gasless nanostructured energetic materials
Uploaded: 2015-04-02T13:00:00
Description: Watch this Scientific Journal Video about Preparation and Reactivity of Gasless Nanostructured Energetic Materials at JoVE.com

This material is based upon work supported by the Department of&#160;Energy, National Nuclear Security Administration,&#160;under Award Number DE-NA0002377. Funding from the Defense Threat Reduction Agency (DTRA), Grant Number HDTRA1-10-1-0119. Counter-WMD basic research program, Dr. Suhithi M. Peiris, program director is gratefully acknowledged. This work was also supported by the Ministry of Education and Science and Education of the Russian Federation in the framework of Increase Competitiveness Program of NUST &#8220;MISIS&#8221; grant No. K2-2014-001.

1. High-energy Ball Milling
<ol>
	<li>Prepare 35 g of the initial 1:1 molar ratio Ni+Al mixture. In this case, weigh 11.02 g of Al and 23.98 g of Ni powders.</li>
	<li>Use a steel milling jar for HEBM of this system. Ensure that the jar has a higher hardness than the powders to be added, otherwise the powders will damage the jar and contamination will arise. Note: Typical jar choices include steel, zirconium oxide, or tungsten carbide.</li>
	<li>Use a 5:1 ball:powder (charge ratio) for this system, i.e., 175 g...

<ol>
	<li>Fried, L. E., Manaa, M. R., Pagoria, P. F., Simpson, R. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Design+and+Synthesis+of+Energetic+Materials.">Design and Synthesis of Energetic Materials.</a> Annual Review of Materials Research. 31, 291-321 (2001).</li><li>Dlott, D. D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Thinking+Big+(and+Small)+about+Energetic+Materials.">Thinking Big (and Small) about Energetic Materials.</a> Materials Science and Technology. 22 (4), 463-473 (2006).</li><li>Dreizin, E. 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B., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Modeling+and+Characterizing+the+Propagation+Velocity+of+Exothermic+Reactions+in+Multilayer+Foils.">Modeling and Characterizing the Propagation Velocity of Exothermic Reactions in Multilayer Foils.</a> Journal of Applied Physics. 82 (3), 1178 (1997).</li><li>Jayaraman, S., Mann, A. B., Reiss, M., Weihs, T. P., Knio, O. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Numerical+Study+of+the+Effect+of+Heat+Losses+on+Self-Propagating+Reactions+in+Multilayer+Foils.">Numerical Study of the Effect of Heat Losses on Self-Propagating Reactions in Multilayer Foils.</a> Combustion and Flame. 124 (1-2), 178-194 (2001).</li><li>Rogachev, A. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Exothermic+Reaction+Waves+in+Multilayer+Nanofilms.">Exothermic Reaction Waves in Multilayer Nanofilms.</a> Russian Chemical Reviews. 77 (1), 21-37 (2008).</li><li>White, J. D. E., Reeves, R. V., Son, S. F., Mukasyan, A. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Thermal+Explosion+in+Al-Ni+System:+Influence+of+Mechanical+Activation.">Thermal Explosion in Al-Ni System: Influence of Mechanical Activation.</a> The Journal of Physical Chemistry A. 113 (48), 13541-13547 (2009).</li><li>Shteinberg, A. S., Lin, Y. -. C., Son, S. F., Mukasyan, A. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Kinetics+of+High+Temperature+Reaction+in+Ni-Al+System:+Influence+of+Mechanical+Activation.">Kinetics of High Temperature Reaction in Ni-Al System: Influence of Mechanical Activation.</a> The Journal of Physical Chemistry A. 114 (20), 6111-6116 (2010).</li><li>Manukyan, K. V., Lin, Y. L., Rouvimov, S., McGinn, P. J., Mukasyan, A. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Microstructure-reactivity+relationship+of+Ti+reactive+nanomaterials.">Microstructure-reactivity relationship of Ti reactive nanomaterials.</a> Journal of Applied Physics. 113 (2), 024302 (2013).</li><li>Mukasyan, A. S., Lin, Y. C., Rogachev, A. S., Moskovskikh, D. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Direct+Combustion+Synthesis+of+Silicon+Carbide+Nanopowder+from+the+Elements.">Direct Combustion Synthesis of Silicon Carbide Nanopowder from the Elements.</a> Journal of the American Ceramic Society. 96 (1), 111-117 (2013).</li><li>Lin, Y. C., Nepapushev, A. A., McGinn, P. J., Rogachev, A. S., Mukasyan, A. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Combustion+joining+of+carbon/carbon+composites+by+a+reactive+mixture+of+titanium+and+mechanically+activated+nickel/aluminum+powders.">Combustion joining of carbon/carbon composites by a reactive mixture of titanium and mechanically activated nickel/aluminum powders.</a> Ceramics International. 39 (7), 7499-7505 (2013).</li><li>Manukyan, K. V., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Tailored+Reactivity+of+Ni+AlNanocomposites:+Microstructural+Correlations.">Tailored Reactivity of Ni+AlNanocomposites: Microstructural Correlations.</a> The Journal of Physical Chemistry C. 116 (39), 21027-21038 (2012).</li><li>Qiu, X., Wang, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Bonding+Silicon+Wafers+with+Reactive+Multilayer+Foils.">Bonding Silicon Wafers with Reactive Multilayer Foils.</a> Sensors and Actuators A. 141 (2), 476-481 (2008).</li><li>Wang, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Joining+of+Stainless-Steel+Specimens+with+Nanostructured+Al/Ni+Foils.">Joining of Stainless-Steel Specimens with Nanostructured Al/Ni Foils.</a> Journal of Applied Physics. 95 (1), 248-256 (2004).</li><li>Rogachev, A. S., Mukasyan, A. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Combustion+of+Heterogeneous+Nanostructural+Systems+(Review).">Combustion of Heterogeneous Nanostructural Systems (Review).</a> Combustion, Explosion, and Shock Waves. (Engl. Transl). 46 (3), 243-266 (2010).</li><li>Granier, J. J., Pantoya, M. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Laser+Ignition+of+Nanocomposite+Thermites).">Laser Ignition of Nanocomposite Thermites).</a> Combustion and Flame. 138 (4), 373-383 (2004).</li><li>Bockmon, B. S., Pantoya, M. L., Son, S. F., Asay, B. W., Mang, J. T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Combustion+Velocities+and+Propagation+Mechanisms+of+Metastable+Interstitial+Composites.">Combustion Velocities and Propagation Mechanisms of Metastable Interstitial Composites.</a> Journal of Applied Physics. 98 (6), 064903-064907 (2005).</li><li>Tillotson, T. M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Nanostructured+Energetic+Materials+Using+Sol&#8722;Gel+Methodologies.">Nanostructured Energetic Materials Using Sol&#8722;Gel Methodologies.</a> Journal of Non-Crystalline Solids. 285 (1-3), 338-345 (2001).</li><li>Cervantes, O. G., Kuntz, J. D., Gash, A. E., Munir, Z. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Heat+of+Combustion+of+Tantalum&#8722;Tungsten+Oxide+Thermite+Composites.">Heat of Combustion of Tantalum&#8722;Tungsten Oxide Thermite Composites.</a> Combustion and Flame. 157 (12), 2326-2332 (2010).</li><li>Leventis, N., Chandrasekaran, N., Sadekar, A. G., Sotiriou-Leventis, C., Lu, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=One-Pot+Synthesis+of+Interpenetrating+Inorganic/Organic+Networks+of+CuO/Resorcinol-Formaldehyde+Aerogels:+Nanostructured+Energetic+Materials.">One-Pot Synthesis of Interpenetrating Inorganic/Organic Networks of CuO/Resorcinol-Formaldehyde Aerogels: Nanostructured Energetic Materials.</a> Journal of the American Chemical Society. 131 (13), 4576-4577 (2009).</li><li>Zhang, K., Rossi, C., Ardila Rodriguez, G. A., Tenailleau, C., Alphonse, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Development+of+a+Nano-Al/CuO+Based+Energetic+Material+on+Silicon+Substrate.">Development of a Nano-Al/CuO Based Energetic Material on Silicon Substrate.</a> Applied Physics Letters. 91 (11), 113117-113113 (2007).</li><li>Xu, D., Yang, Y., Cheng, H., Li, Y. Y., Zhang, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Integration+of+Nano-Al+with+Co3O4Nanorods+to+Realize+High-Exothermic+Core-Shell+Nanoenergetic+Materials+on+a+Silicon+Substrate.">Integration of Nano-Al with Co3O4Nanorods to Realize High-Exothermic Core-Shell Nanoenergetic Materials on a Silicon Substrate.</a> Combustion and Flame. 159 (6), 2202-2209 (2012).</li><li>Shearing, P. R., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Exploring+Microstructural+Changes+Assicuated+with+Oxidation+in+Ni-YSZ+SOFC+Electrodes+Using+High+Resolution+X-ray+Computed+Tomography.">Exploring Microstructural Changes Assicuated with Oxidation in Ni-YSZ SOFC Electrodes Using High Resolution X-ray Computed Tomography.</a> Solid State Ionics. 216 (28), 69-72 (2012).</li><li>Bacciochini, A., Bourdon-Lafleur, S., Poupart, C., Radulescu, M., Ni-Al, J. o. d. o. i. n. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Nanoscale+Energetic+Materials:+Phenomena+Involved+During+the+Manufacturing+of+Bulk+Samples+by+Cold+Spray.">Nanoscale Energetic Materials: Phenomena Involved During the Manufacturing of Bulk Samples by Cold Spray.</a> Journal of Thermal Spray Technology. In press, (2014).</li></ol>

The protocol provides a detailed description for preparation of reactive energetic (Ti+C, Ta+C, Ni+Al) nanocomposites with tailored microstructure by using the short-term HEBM method. HEBM of gasless heterogeneous mixtures involve their processing in a high-speed planetary ball mill, where the particles of the mixture are subjected to mechanical impact with a force sufficient for breakdown of brittle components (e.g. graphite) and deformation of plastic components (e.g., Al, Ti, Ta, Ni). Brittle reactan...

Classical energetic materials, i.e., explosives, propellants and pyrotechnics are a class of material with a high amount of stored chemical energy that can be released during rapid exothermic reaction1-5. For example, explosives are usually generated by combining fuel and oxidizer groups into one molecule. The energy density of those materials is very high. For example, upon decomposition trinitrotoluene (TNT) releases 7.22 kJ/cm3 and forms 8.36 moles of gases per 100 g (Table 1) in a very short period of time. These materials are composed of micrometer-scale organic and inorganic species (fuels and oxidizers).
Thermite systems, where reactions take place between the inorganic compound, i.e., reducing metals (e.g., Al) and oxides (Fe2O3, CuO, Bi2O3), belong to another type of energetic materials. The energy density (15-21 kJ/cm3) of such systems exceeds that of TNT, however the amount of gas products (0.15-0.6 moles per 100 g) is typically much less than for explosives (Table 1). Also, the nano-thermites may show extremely high velocity of combustion wave propagation (&#62;1,000 m/sec)2-5.
It was recently shown6-12 that a number of gasless heterogeneous reactive systems (Ni+Al, Ti+C, Ti+B) that form intermetallic or refractory compounds could also be considered as energetic materials. The energy densities (kJ/cm3) of those systems are closer or higher than that of TNT (Table 1). At the same time, the absence of gas products during the reaction makes such materials excellent candidates for a variety of applications including synthesis of nanomaterials, reactive bonding of refractory and dissimilar parts, gasless micro power generators, etc.11-17. However, the relatively high ignition temperature of those systems (900-3,000 K, see Table 1) compared to thermites (~1,000 K) hinders their applications. The preparation of engineered nanostructured composites could significantly enhance the ignition and combustion characteristics of gasless heterogeneous systems12-14, 17.
Many methods have been developed to fabricate the engineered energetic nanocomposites, such as ultrasonic mixing18,19, self-assembly approaches5, sol-gel20-22, vapor deposition techniques16,17,23,24, as well as high-energy ball milling (HEBM)1,5. The disadvantage of ultrasonic mixing of nano-powder is that a thick (5-10 nm) oxide shell on metal nanoparticles reduces energy density and degrades the combustion performance of reactive mixtures. Also, the distribution of fuel and oxidizer is not uniform, and the interfacial contact between reactants is not intimate. Sol-gel and self-assembly strategies were developed for preparation of specific thermite nanocomposites. Despite being low-cost techniques, those strategies are not green from an environmental standpoint. Moreover, large amounts of impurities are introduced into prepared composites. Vapor deposition or magnetron sputtering is used to prepare reactive multi-layer foils and core-shell energetic materials. It provides a pore-free and well-defined geometry of composites that simplifies theoretical modeling and enhances accuracy. However, this technology is expensive and difficult to scale up. Furthermore, the prepared layered nanocomposites are unstable in certain conditions.
High-Energy Ball Milling (HEBM) is an environmentally friendly, easily scalable approach that allows effective fabrication of nanostructured energetic composites5,9-14. HEBM is inexpensive and can be used with various reactive material compositions (e.g., thermites, reactions that form intermetallics, carbides, borides, etc.).
The protocol provides a detailed description for preparation of reactive energetic (Ni+Al, Ti+C, Ta+C) nanocomposites with tailored microstructure by using the short-term HEBM method. It also describes a high-speed thermal imaging technique to determine the ignition/combustion characteristics of as-fabricated energetic materials. Finally it shows the analysis of the microstructure of the nanocomposites using Field Emission Scanning Electron Microscope (FESEM) Equipped by Focused Ion Beam (FIB). The protocol is an important guide for the preparation of different energetic nanomaterials (gasless and thermite systems) that could be used as either high energy density sources or for synthesis and processing of advanced nanomaterials by combustion-based approaches.

<table border="0" cellpadding="0" cellspacing="0">
	<tbody>
		<tr>
			<td>Titanium</td>
			<td>Alfa Aesar</td>
			<td>42624</td>
			<td>Particle size: -325 mesh</td>
			<td>Purity, 99.5%</td>
		</tr>
		<tr>
			<td>Graphite</td>
			<td>Alfa Aesar</td>
			<td>46304</td>
			<td>Particle size: 7-11 micron</td>
			<td>Purity, 99%</td>
		</tr>
		<tr>
			<td>Nickel</td>
			<td>Alfa Aesar</td>
			<td>10256</td>
			<td>Particle size: 3-7 micron</td>
			<td>Purity, 99.9%</td>
		</tr>
		<tr>
			<td>Aluminum</td>
			<td>Alfa Aesar</td>
			<td>11067</td>
			<td>Particle size: -325 mesh</td>
			<td>Purity, 99.5%</td>
		</tr>
		<tr>
			<td>Tantalum</td>
			<td>Materion advanced chemicals</td>
			<td>T-2017</td>
			<td>Particle size: 325 mesh</td>
			<td>Purity, 99.9%</td>
		</tr>
		<tr>
			<td>Carbon lampblack</td>
			<td>Fisher scientific</td>
			<td>C198-500</td>
			<td>Particle size: 0.1 micron</td>
			<td>Purity, 99.9%</td>
		</tr>
		<tr>
			<td>Tungsten wire</td>
			<td>Mcmaster Carr</td>
			<td>n/a</td>
			<td>0.032&#34; diameter</td>
			<td>n/a</td>
		</tr>
		<tr>
			<td>Planetary Ball Mill</td>
			<td>Retsch GmbH, Germany</td>
			<td>n/a</td>
			<td>n/a</td>
			<td>n/a</td>
		</tr>
		<tr>
			<td>Uniaxial press</td>
			<td>Carver Hydraulic</td>
			<td>n/a</td>
			<td>n/a</td>
			<td>n/a</td>
		</tr>
		<tr>
			<td>Sieve shaker</td>
			<td>Gilson performer</td>
			<td>n/a</td>
			<td>5mm diameter</td>
			<td>n/a</td>
		</tr>
		<tr>
			<td>Cylindrical stainless steel press die</td>
			<td>Action Machine</td>
			<td>n/a</td>
			<td>n/a</td>
			<td>n/a</td>
		</tr>
		<tr>
			<td>Stainless steel sieves</td>
			<td>Mcmaster Carr</td>
			<td>Type 304</td>
			<td>n/a</td>
			<td>n/a</td>
		</tr>
		<tr>
			<td>High-speed thermal camera (SC6000)</td>
			<td>FLIR</td>
			<td>n/a</td>
			<td>n/a</td>
			<td>n/a</td>
		</tr>
		<tr>
			<td>Helios NanoLab 600, Field Emission Scanning Electron Microscope (FESEM) Equipped by Focus Ion Beam (FIB)</td>
			<td>FEI</td>
			<td>n/a</td>
			<td>n/a</td>
			<td>n/a</td>
		</tr>
		<tr>
			<td>Cylindrical reactor with a vacuum pomp</td>
			<td>Action Machine</td>
			<td>n/a</td>
			<td>n/a</td>
			<td>n/a</td>
		</tr>
		<tr>
			<td>Autoslice and View (S&#38;V)</td>
			<td>FEI</td>
			<td>n/a</td>
			<td>n/a</td>
			<td>n/a</td>
		</tr>
		<tr>
			<td>Avizo Fire</td>
			<td>FEI</td>
			<td>n/a</td>
			<td>n/a</td>
			<td>n/a</td>
		</tr>
	</tbody>
</table>

preparation and reactivity of gasless nanostructured energetic materials

High-Energy Ball Milling (HEBM) is a ball milling process where a powder mixture placed in the ball mill is subjected to high-energy collisions from the balls. Among other applications, it is a versatile technique that allows for effective preparation of gasless reactive nanostructured materials with high energy density per volume (Ni+Al, Ta+C, Ti+C). The structural transformations of reactive media, which take place during HEBM, define the reaction mechanism in the produced energetic&#160;composites. Varying the processing conditions permits fine tuning of the milling-induced microstructures of the fabricated composite particles. In turn, the reactivity, i.e., self-ignition temperature, ignition delay time, as well as reaction kinetics, of high energy density materials depends on its microstructure. Analysis of the milling-induced microstructures suggests that the formation of fresh oxygen-free intimate high surface area contacts between the reagents is responsible for the enhancement of their reactivity. This manifests itself in a reduction of ignition temperature and delay time, an increased rate of chemical reaction, and an overall decrease of the effective activation energy of the reaction. The protocol provides a detailed description for the preparation of reactive nanocomposites with tailored microstructure using short-term HEBM method. It also describes a high-speed thermal imaging technique to determine the ignition/combustion characteristics of the energetic materials. The protocol can be adapted to preparation and characterization of a variety of nanostructured energetic composites.

To prepare nanostructured energetic composites, a mixture of desired powdered components (typically micrometer-sized) is mechanically treated under preset milling conditions. Processing time (typically minutes) is accurately controlled to generate the compositionally homogenized nanocomposite particles but not permitting the self-sustaining chemical reaction to initiate during milling.
Figure 1 and Video 1 show that contact surface area between the reactants i...

Watch this Scientific Journal Video about Preparation and Reactivity of Gasless Nanostructured Energetic Materials at JoVE.com

Preparation and Reactivity of Gasless Nanostructured Energetic Materials

This protocol describes the preparation of gasless nanostructured energetic materials (Ni+Al, Ta+C, Ti+C) using the short-term high-energy ball milling (HEBM) technique. It also describes a high-speed thermal imaging method to study the reactivity of mechanically fabricated nanocomposites. These protocols can be extended to other reactive nanostructured energetic materials.

High-Energy Ball Milling (HEBM) is a ball milling process where a powder mixture placed in the ball mill is subjected to high-energy collisions from the ...

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Construction and Testing of Coin Cells of Lithium Ion Batteries

Rechargeable lithium ion batteries have wide applications in electronics, where customers always demand more capacity and longer lifetime. Lithium ion batteries have also been considered to be used in electric and hybrid vehicles1 or even electrical grid stabilization systems2. All these applications simulate a dramatic increase in the research and development of battery materials3-7, including new materials3,8, doping9, nanostructuring10-13, coatings or surface modifications14-17 and novel binders18. Consequently, an increasing number of physicists, chemists and materials scientists have recently ventured into this area. Coin cells are widely used in research laboratories to test new battery materials; even for the research and development that target large-scale and high-power applications, small coin cells are often used to test the capacities and rate capabilities of new materials in the initial stage. 
 In 2010, we started a National Science Foundation (NSF) sponsored research project to investigate the surface adsorption and disordering in battery materials (grant no. DMR-1006515). In the initial stage of this project, we have struggled to learn the techniques of assembling and testing coin cells, which cannot be achieved without numerous help of other researchers in other universities (through frequent calls, email exchanges and two site visits). Thus, we feel that it is beneficial to document, by both text and video, a protocol of assembling and testing a coin cell, which will help other new researchers in this field. This effort represents the "Broader Impact" activities of our NSF project, and it will also help to educate and inspire students.
In this video article, we document a protocol to assemble a CR2032 coin cell with a LiCoO2 working electrode, a Li counter electrode, and (the mostly commonly used) polyvinylidene fluoride (PVDF) binder. To ensure new learners to readily repeat the protocol, we keep the protocol as specific and explicit as we can. However, it is important to note that in specific research and development work, many parameters adopted here can be varied. First, one can make coin cells of different sizes and test the working electrode against a counter electrode other than Li. Second, the amounts of C black and binder added into the working electrodes are often varied to suit the particular purpose of research; for example, large amounts of C black or even inert powder were added to the working electrode to test the "intrinsic" performance of cathode materials14. Third, better binders (other than PVDF) have also developed and used18. Finally, other types of electrolytes (instead of LiPF6) can also be used; in fact, certain high-voltage electrode materials will require the uses of special electrolytes7.

A protocol to construct and test coin cells of lithium ion batteries is described. The specific procedures of making a working electrode, preparing a counter electrode, assembling a cell inside a glovebox and testing the cell are presented.

Rechargeable lithium ion batteries have wide applications in electronics, where customers always demand more capacity and longer lifetime.  Lithium ion ...

Nanomoulding of Functional Materials, a Versatile Complementary Pattern Replication Method to Nanoimprinting

We describe a nanomoulding technique which allows low-cost nanoscale patterning of functional materials, materials stacks and full devices. Nanomoulding combined with layer transfer enables the replication of arbitrary surface patterns from a master structure onto the functional material. Nanomoulding can be performed on any nanoimprinting setup and can be applied to a wide range of materials and deposition processes. In particular we demonstrate the fabrication of patterned transparent zinc oxide electrodes for light trapping applications in solar cells.

We describe a nanomoulding technique which allows low-cost nanoscale patterning of functional materials, materials stacks and full devices. Nanomoulding can be performed on any nanoimprinting setup and can be applied to a wide range of materials and deposition processes.

We describe a nanomoulding technique which  allows low-cost nanoscale patterning of functional materials, materials stacks  and full devices. Nanomoulding ...

Concurrent Quantitative Conductivity and Mechanical Properties Measurements of Organic Photovoltaic Materials using AFM

Organic photovoltaic (OPV) materials are inherently inhomogeneous at the nanometer scale. Nanoscale inhomogeneity of OPV materials affects performance of photovoltaic devices. Thus, understanding of spatial variations in composition as well as electrical properties of OPV materials is of paramount importance for moving PV technology forward.1,2 In this paper, we describe a protocol for quantitative measurements of electrical and mechanical properties of OPV materials with sub-100 nm resolution. Currently, materials properties measurements performed using commercially available AFM-based techniques (PeakForce, conductive AFM) generally provide only qualitative information. The values for resistance as well as Young's modulus measured using our method on the prototypical ITO/PEDOT:PSS/P3HT:PC61BM system correspond well with literature data. The P3HT:PC61BM blend separates onto PC61BM-rich and P3HT-rich domains. Mechanical properties of PC61BM-rich and P3HT-rich domains are different, which allows for domain attribution on the surface of the film. Importantly, combining mechanical and electrical data allows for correlation of the domain structure on the surface of the film with electrical properties variation measured through the thickness of the film.

Organic photovoltaic (OPV) materials are inherently inhomogeneous at the nanometer scale. Nanoscale inhomogeneity of OPV materials affects performance of photovoltaic devices. In this paper, we describe a protocol for quantitative measurements of electrical and mechanical properties of OPV materials with sub-100 nm resolution.

Organic photovoltaic  (OPV) materials are inherently inhomogeneous at the nanometer scale. Nanoscale  inhomogeneity of OPV materials affects performance ...

Preparation and Friction Force Microscopy Measurements of Immiscible, Opposing Polymer Brushes

Solvated polymer brushes are well known to lubricate high-pressure contacts, because they can sustain a positive normal load while maintaining low friction at the interface. Nevertheless, these systems can be sensitive to wear due to interdigitation of the opposing brushes. In a recent publication, we have shown via molecular dynamics simulations and atomic force microscopy experiments, that using an immiscible polymer brush system terminating the substrate and the slider surfaces, respectively, can eliminate such interdigitation. As a consequence, wear in the contacts is reduced. Moreover, the friction force is two orders of magnitude lower compared to traditional miscible polymer brush systems. This newly proposed system therefore holds great potential for application in industry. Here, the methodology to construct an immiscible polymer brush system of two different brushes each solvated by their own preferred solvent is presented. The procedure how to graft poly(N-isopropylacrylamide) (PNIPAM) from a flat surface and poly(methyl methacrylate) (PMMA) from an atomic force microscopy (AFM) colloidal probe is described. PNIPAM is solvated in water and PMMA in acetophenone. Via friction force AFM measurements, it is shown that the friction for this system is indeed reduced by two orders of magnitude compared to the miscible system of PMMA on PMMA solvated in acetophenone.

The methodology to perform friction force microscopy experiments for contacting brushes is presented: Two polymer brushes that are grafted from (a) substrates and (b) colloidal probes are slid to show that, by using two contacting immiscible brush systems, friction in sliding contacts is reduced compared to miscible brush systems.

Solvated polymer brushes are well known to lubricate high-pressure contacts, because they can sustain a positive normal load while maintaining low ...

Surface Enhanced Raman Spectroscopy Detection of Biomolecules Using EBL Fabricated Nanostructured Substrates

Fabrication and characterization of conjugate nano-biological systems interfacing metallic nanostructures on solid supports with immobilized biomolecules is reported. The entire sequence of relevant experimental steps is described, involving the fabrication of nanostructured substrates using electron beam lithography, immobilization of biomolecules on the substrates, and their characterization utilizing surface-enhanced Raman spectroscopy (SERS). Three different designs of nano-biological systems are employed, including protein A, glucose binding protein, and a dopamine binding DNA aptamer. In the latter two cases, the binding of respective ligands, D-glucose and dopamine, is also included. The three kinds of biomolecules are immobilized on nanostructured substrates by different methods, and the results of SERS imaging are reported. The capabilities of SERS to detect vibrational modes from surface-immobilized proteins, as well as to capture the protein-ligand and aptamer-ligand binding are demonstrated. The results also illustrate the influence of the surface nanostructure geometry, biomolecules immobilization strategy, Raman activity of the molecules and presence or absence of the ligand binding on the SERS spectra acquired.

We describe the fabrication and characterization of nano-biological systems interfacing nanostructured substrates with immobilized proteins and aptamers. The relevant experimental steps involving lithographic fabrication of nanostructured substrates, bio-functionalization, and surface-enhanced Raman spectroscopy (SERS) characterization, are reported. SERS detection of surface-immobilized proteins, and probing of protein-ligand and aptamer-ligand binding is demonstrated.

Fabrication and characterization of conjugate nano-biological systems interfacing metallic nanostructures on solid supports with immobilized biomolecules ...

Synthesis and Functionalization of 3D Nano-graphene Materials: Graphene Aerogels and Graphene Macro Assemblies

Efforts to assemble graphene into three-dimensional monolithic structures have been hampered by the high cost and poor processability of graphene. Additionally, most reported graphene assemblies are held together through physical interactions (e.g., van der Waals forces) rather than chemical bonds, which limit their mechanical strength and conductivity. This video method details recently developed strategies to fabricate mass-producible, graphene-based bulk materials derived from either polymer foams or single layer graphene oxide. These materials consist primarily of individual graphene sheets connected through covalently bound carbon linkers. They maintain the favorable properties of graphene such as high surface area and high electrical and thermal conductivity, combined with tunable pore morphology and exceptional mechanical strength and elasticity. This flexible synthetic method can be extended to the fabrication of polymer/carbon nanotube (CNT) and polymer/graphene oxide (GO) composite materials. Furthermore, additional post-synthetic functionalization with anthraquinone is described, which enables a dramatic increase in charge storage performance in supercapacitor applications.

This video method describes the synthesis of high surface area, monolithic 3D graphene-based materials derived from polymer precursors as well as single layer graphene oxide.

Efforts to assemble graphene into three-dimensional monolithic structures have been hampered by the high cost and poor processability of graphene. ...

Advanced Experimental Methods for Low-temperature Magnetotransport Measurement of Novel Materials

Novel electronic materials are often produced for the first time by synthesis processes that yield bulk crystals (in contrast to single crystal thin film synthesis) for the purpose of exploratory materials research. Certain materials pose a challenge wherein the traditional bulk Hall bar device fabrication method is insufficient to produce a measureable device for sample transport measurement, principally because the single crystal size is too small to attach wire leads to the sample in a Hall bar configuration. This can be, for example, because the first batch of a new material synthesized yields very small single crystals or because flakes of samples of one to very few monolayers are desired. In order to enable rapid characterization of materials that may be carried out in parallel with improvements to their growth methodology, a method of device fabrication for very small samples has been devised to permit the characterization of novel materials as soon as a preliminary batch has been produced. A slight variation of this methodology is applicable to producing devices using exfoliated samples of two-dimensional materials such as graphene, hexagonal boron nitride (hBN), and transition metal dichalcogenides (TMDs), as well as multilayer heterostructures of such materials. Here we present detailed protocols for the experimental device fabrication of fragments and flakes of novel materials with micron-sized dimensions onto substrate and subsequent measurement in a commercial superconducting magnet, dry helium close-cycle cryostat magnetotransport system at temperatures down to 0.300 K and magnetic fields up to 12 T.

We describe the methodology of mechanical exfoliation and deposition of flakes of novel materials with micron-sized dimensions onto substrate, fabrication of experimental device structures for transport experimentation, and the magnetotransport measurement in a dry helium close-cycle cryostat at temperatures down to 0.300 K and magnetic fields up to 12 T.

Novel electronic materials are often produced for the first time by synthesis processes that yield bulk crystals (in contrast to single crystal thin film ...

Nanostructured Ag-zeolite Composites as Luminescence-based Humidity Sensors

Small silver clusters confined inside zeolite matrices have recently emerged as a novel type of highly luminescent materials. Their emission has high external quantum efficiencies (EQE) and spans the whole visible spectrum. It has been recently reported that the UV excited luminescence of partially Li-exchanged sodium Linde type A zeolites [LTA(Na)] containing luminescent silver clusters can be controlled by adjusting the water content of the zeolite. These samples showed a dynamic change in their emission color from blue to green and yellow upon an increase of the hydration level of the zeolite, showing the great potential that these materials can have as luminescence-based humidity sensors at the macro and micro scale. Here, we describe the detailed procedure to fabricate a humidity sensor prototype using silver-exchanged zeolite composites. The sensor is produced by suspending the luminescent Ag-zeolites in an aqueous solution of polyethylenimine (PEI) to subsequently deposit a film of the material onto a quartz plate. The coated plate is subjected to several hydration/dehydration cycles to show the functionality of the sensing film.

A protocol for the synthesis of moisture-responsive luminescent Ag-zeolite composites is described in this report.

Small silver clusters confined inside zeolite matrices have recently emerged as a novel type of highly luminescent materials. Their emission has high ...

High Temperature Fabrication of Nanostructured Yttria-Stabilized-Zirconia (YSZ) Scaffolds by In Situ Carbon Templating Xerogels

We demonstrate a method for the high temperature fabrication of porous, nanostructured yttria-stabilized-zirconia (YSZ, 8 mol% yttria - 92 mol% zirconia) scaffolds with tunable specific surface areas up to 80 m2&#183;g-1. An aqueous solution of a zirconium salt, yttrium salt, and glucose is mixed with propylene oxide (PO) to form a gel. The gel is dried under ambient conditions to form a xerogel. The xerogel is pressed into pellets and then sintered in an argon atmosphere. During sintering, a YSZ ceramic phase forms and the organic components decompose, leaving behind amorphous carbon. The carbon formed in situ serves as a hard template, preserving a high surface area YSZ nanomorphology at sintering temperature. The carbon is subsequently removed by oxidation in air at low temperature, resulting in a porous, nanostructured YSZ scaffold. The concentration of the carbon template and the final scaffold surface area can be systematically tuned by varying the glucose concentration in the gel synthesis. The carbon template concentration was quantified using thermogravimetric analysis (TGA), the surface area and pore size distribution was determined by physical adsorption measurements, and the morphology was characterized using scanning electron microscopy (SEM). Phase purity and crystallite size was determined using X-ray diffraction (XRD). This fabrication approach provides a novel, flexible platform for realizing unprecedented scaffold surface areas and nanomorphologies for ceramic-based electrochemical energy conversion applications, e.g. solid oxide fuel cell (SOFC) electrodes.

High Temperature Fabrication of Nanostructured Yttria-Stabilized-Zirconia YSZ Scaffolds by In Situ Carbon Templating Xerogels

A protocol for fabricating porous, nanostructured yttria-stabilized-zirconia (YSZ) scaffolds at temperatures between 1,000 &#176;C and 1,400 &#176;C is presented.

We demonstrate a method for the high temperature fabrication of porous, nanostructured yttria-stabilized-zirconia (YSZ, 8 mol% yttria - 92 mol% zirconia) ...

Characterization of Ultra-fine Grained and Nanocrystalline Materials Using Transmission Kikuchi Diffraction

One of the challenges in microstructure analysis nowadays resides in the reliable and accurate characterization of ultra-fine grained (UFG) and nanocrystalline materials. The traditional techniques associated with scanning electron microscopy (SEM), such as electron backscatter diffraction (EBSD), do not possess the required spatial resolution due to the large interaction volume between the electrons from the beam and the atoms of the material. Transmission electron microscopy (TEM) has the required spatial resolution. However, due to a lack of automation in the analysis system, the rate of data acquisition is slow which limits the area of the specimen that can be characterized. This paper presents a new characterization technique, Transmission Kikuchi Diffraction (TKD), which enables the analysis of the microstructure of UFG and nanocrystalline materials using an SEM equipped with a standard EBSD system. The spatial resolution of this technique can reach 2 nm. This technique can be applied to a large range of materials that would be difficult to analyze using traditional EBSD. After presenting the experimental set up and describing the different steps necessary to realize a TKD analysis, examples of its use on metal alloys and minerals are shown to illustrate the resolution of the technique and its flexibility in term of material to be characterized.

This paper provides a detailed method to characterize the microstructure of ultra-fine grained and nanocrystalline materials using a scanning electron microscope equipped with a standard electron backscatter diffraction system. Metal alloys and minerals presenting refined microstructures are analyzed using this technique, showing the diversity of its possible applications.