Matthew E. Staymates

Dropwise Condensation of Low Surface Tension Fluids on Omniphobic Surfaces

Compared to the significant body of work devoted to surface engineering for promoting dropwise condensation heat transfer of steam, much less attention has been dedicated to fluids with lower interfacial tension. A vast array of low-surface tension fluids such as hydrocarbons, cryogens, and fluorinated refrigerants are used in a number of industrial applications, and the development of passive means for increasing their condensation heat transfer coefficients has potential for significant efficiency enhancements. Here we investigate condensation behavior of a variety of liquids with surface tensions in the range of 12 to 28u2005mN/m on three types of omniphobic surfaces: smooth oleophobic, re-entrant superomniphobic, and lubricant-impregnated surfaces. We demonstrate that although smooth oleophobic and lubricant-impregnated surfaces can promote dropwise condensation of the majority of these fluids, re-entrant omniphobic surfaces became flooded and reverted to filmwise condensation. We also demonstrate that on the lubricant-impregnated surfaces, the choice of lubricant and underlying surface texture play a crucial role in stabilizing the lubricant and reducing pinning of the condensate. With properly engineered surfaces to promote dropwise condensation of low-surface tension fluids, we demonstrate a four to eight-fold improvement in the heat transfer coefficient.

Dynamics of silver nanoparticle release from wound dressings revealed via in situ nanoscale imaging

The use of silver nanoparticles (AgNPs) in textiles for enhanced anti-microbial properties has led to concern about their release and impact on both human and environmental health. Here a novel method for in situ visualization of AgNP release from silver-impregnated wound dressings is introduced. By combining an environmental scanning electron microscope, a gaseous analytical detector and a peltier cooling stage, this technique provides near-instantaneous nanoscale characterization of interactions between individual water droplets and AgNPs. We show that dressings with different silver application methods have very distinct AgNP release dynamics. Specifically, water condensation on dressings with AgNP deposited directly on the fiber surface resulted in substantial and rapid AgNP release. By comparison, AgNP release from wound dressing with nanoparticles grown, not deposited, from the fiber surface was either much slower or negligible. Our methodology complements standard bulk techniques for studying of silver release from fabrics by providing dynamic nanoscale information about mechanisms governing AgNP release from individual fibers. Thus coupling these nano and macro-scale methods can provide insight into how the wound dressing fabrication could be engineered to optimize AgNP release for different applications.

Rapid analysis of trace drugs and metabolites using a thermal desorption DART-MS configuration

The need to analyze trace narcotic samples rapidly for screening or confirmatory purposes is of increasing interest to the forensic, homeland security, and criminal justice sectors. This work presents a novel method for the detection and quantification of trace drugs and metabolites off of a swipe material using a thermal desorption direct analysis in real time mass spectrometry (TD-DART-MS) configuration. A variation on traditional DART, this configuration allows for desorption of the sample into a confined tube, completely independent of the DART source, allowing for more efficient and thermally precise analysis of material present on a swipe. Over thirty trace samples of narcotics, metabolites, and cutting agents deposited onto swipes were rapidly differentiated using this methodology. The non-optimized method led to sensitivities ranging from single nanograms to hundreds of picograms. Direct comparison to traditional DART with a subset of the samples highlighted an improvement in sensitivity by a factor of twenty to thirty and an increase in reproducibility sample to sample from approximately 45 % RSD to less than 15 % RSD. Rapid extraction-less quantification was also possible.

Evaluation of a drop-on-demand micro-dispensing system for development of artificial fingerprints

Precision micro-dispensing is an evolving technique that has many applications in the scientific and additive manufacturing communities. Here we describe a method for dispensing viscous materials, including the oily substance found in human fingerprints, known as sebum. In this work, a dispense jet system was used to deposit known amounts of sebum onto surfaces to represent an artificial human fingerprint. Ultraviolet-visible spectrophotometry (UV-Vis) and microgravimetry were used to verify the sebum mass loadings of the samples. The dispense jet was capable of printing a viscous sebum mixture as well as a less viscous solution of sebum dissolved in heptane. This method was shown to be repeatable, and UV-Vis was found to be a simple and useful technique for verifying the mass of sebum deposited. This method could be used to prepare artificial fingerprint samples for a variety of applications including the preparation of test materials for emerging trace detection technologies.

Production and characterization of polymer microspheres containing trace explosives using precision particle fabrication technology.

Well characterized test materials are essential for validating the performance of current trace explosive detection systems. These test materials must replicate trace explosive contamination in the form of small particles with characteristic diameters in the micrometer range. In this work, Precision Particle Fabrication was used to fabricate monodisperse polymer microspheres that contain high explosives. Three high explosives were successfully incorporated into the microspheres. Ion mobility spectrometry confirmed that the encapsulation efficiency was typically greater than 50%, with some suspected loss to the aqueous phase during production. This study demonstrates that, with this technique, polymer microspheres containing explosives can be produced with sufficient encapsulation, along with tightly controlled particle size distributions at high production rates. These microspheres have proven to be a valuable test material for trace explosive detectors because of their highly precise size, shape and explosive composition.

DART-MS analysis of inorganic explosives using high temperature thermal desorption

An ambient mass spectrometry (MS) platform coupling resistive Joule heating thermal desorption (JHTD) and direct analysis in real time (DART) was implemented for the analysis of inorganic nitrite, nitrate, chlorate, and perchlorate salts. The resistive heating component generated discrete and rapid heating ramps and elevated temperatures, up to approximately 400 °C s-1 and 750 °C, by passing a few amperes of DC current through a nichrome wire. JHTD enhanced the utility and capabilities of traditional DART-MS for the trace detection of previously difficult to detect inorganic compounds. A partial factorial design of experiments (DOE) was implemented for the systematic evaluation of five system parameters. A base set of conditions for JHTD-DART-MS was derived from this evaluation, demonstrating sensitive detection of a range of inorganic oxidizer salts, down to single nanogram levels. DOE also identified JHTD filament current and in-source collision induced dissociation (CID) energy as inducing the greatest effect on system response. Tuning of JHTD current provided a method for controlling the relative degrees of thermal desorption and thermal decomposition. Furthermore, in-source CID provided manipulation of adduct and cluster fragmentation, optimizing the detection of molecular anion species. Finally, the differential thermal desorption nature of the JHTD-DART platform demonstrated efficient desorption and detection of organic and inorganic explosive mixtures, with each desorbing at its respective optimal temperature.

Enhanced aerodynamic reach of vapor and aerosol sampling for real-time mass spectrometric detection using Venturi-assisted entrainment and ionization ☆

Venturi-assisted ENTrainment and Ionization (VENTI) was developed, demonstrating efficient entrainment, collection, and transport of remotely sampled vapors, aerosols, and dust particulate for real-time mass spectrometry (MS) detection. Integrating the Venturi and Coandă effects at multiple locations generated flow and analyte transport from non-proximate locations and more importantly enhanced the aerodynamic reach at the point of collection. Transport through remote sampling probes up to 2.5xa0m in length was achieved with residence times on the order of 10-2xa0s to 10-1xa0s and Reynolds numbers on the order of 103 to 104. The Venturi-assisted entrainment successfully enhanced vapor collection and detection by greater than an order of magnitude at 20xa0cm stand-off (limit of simple suction). This enhancement is imperative, as simple suction restricts sampling to the immediate vicinity, requiring close proximity to the vapor source. In addition, the overall aerodynamic reach distance was increased by approximately 3-fold over simple suction under the investigated conditions. Enhanced aerodynamic reach was corroborated and observed with laser-light sheet flow visualization and schlieren imaging. Coupled with atmospheric pressure chemical ionization (APCI), the detection of a range of volatile chemical vapors; explosive vapors; explosive, narcotic, and mustard gas surrogate (methyl salicylate) aerosols; and explosive dust particulate was demonstrated. Continuous real-time Venturi-assisted monitoring of a large room (approximately 90xa0m2 area, 570xa0m3 volume) was demonstrated for a 60-min period without the remote sampling probe, exhibiting detection of chemical vapors and methyl salicylate at approximately 3xa0m stand-off distances within 2xa0min of exposure.

The effect of reusing wipes for particle collection

Sample collection for Ion Mobility Spectrometry (IMS) analysis is typically completed by swiping a collection wipe over a suspect surface to collect trace residues. The work presented here addresses the need for a method to measure the collection efficiency performance of surface wipe materials as a function of the number of times a wipe is used to interrogate a surface. The primary purpose of this study is to investigate the effect of wipe reuse, i.e., the number of times a wipe is swiped across a surface, on the overall particle collection and IMS response. Two types of collection wipes (Teflon coated fiberglass and Nomex) were examined by swiping multiple times, ranging from 0 to 1000, over representative surfaces that are common to security screening environments. Particle collection efficiencies were determined by fluorescence microscopy and particle counting techniques, and were shown to improve dramatically with increased number of swiping cycles. Ion mobility spectrometry was used to evaluate the chemical response of known masses of explosives (deposited after reusing wipes) as a function of the wipe reuse number. Results show that chemical response can be negatively affected, and greatly depends upon the conditions of the surface in which the wipe is interrogating. For most parameters tested, the PCE increased after the wipe was reused several times. Swiping a dusty cardboard surface multiple times also caused an increase in particle collection efficiency but a decrease in IMS response. Scanning electron microscopy images revealed significant surface degradation of the wipes on dusty cardboard at the micrometer spatial scale level for Teflon coated wipes. Additionally, several samples were evaluated by including a seven second thermal desorption cycle at 235°C into each swipe sampling interval in order to represent the IMS heating cycle. Results were similar to studies conducted without this heating cycle, suggesting that the primary mechanism for wipe deterioration is mechanical rather than thermal.

The production of monodisperse explosive particles with piezo-electric inkjet printing technology

We have developed a method to produce discrete microparticles from compounds dissolved in nonpolar or polar solvents using drop-on-demand inkjet printer technology. A piezoelectric inkjet printhead located atop a drying tube produces precise droplets containing defined quantities of analyte. Droplets solidify into microparticles with known composition and size as they traverse down the drying tube. Because this is a drop-on-demand printing process, a known number of droplets are produced providing quantitative particle delivery to a variety of substrates. Particular emphasis is placed on the development and characterization of the drying tube in this work. The drying tube was modeled using computational fluid dynamics and experimentally evaluated using laser-based flow visualization techniques. A notable design feature of the drying tube is the ability to push heated air through the tube rather than the need to pull air from the exit. This provides the ability to place a known number of well-defined particles onto almost any substrate of interest, rather than having to collect particles onto a filter first and then transfer them to another surface. Several types of particles have been produced by this system, examples of which are pure particles of cyclotrimethylenetrinitramine ranging from 10 μm to 30 μm in diameter, and ammonium nitrate particles of 40 μm diameter. The final particle size is directly related to the solute concentration of the printing solution and the size of the initial jetted droplet.

Nanoporous Silicon Combustion: Observation of Shock Wave and Flame Synthesis of Nanoparticle Silica

The persistent hydrogen termination present in nanoporous silicon (nPS) is unique compared to other forms of nanoscale silicon (Si) which typically readily form a silicon dioxide passivation layer. The hydrogen terminated surface combined with the extremely high surface area of nPS yields a material capable of powerful exothermic reactions when combined with strong oxidizers. Here, a galvanic etching mechanism is used to produce nPS both in bulk Si wafers as well as in patterned regions of Si wafers with microfabricated ignition wires. An explosive composite is generated by filling the pores with sodium perchlorate (NaClO4). Using high-speed video including Schlieren photography, a shock wave is observed to propagate through air at 1127 ± 116 m/s. Additionally, a fireball is observed above the region of nPS combustion which persists for nearly 3× as long when reacted in air compared to N2, indicating that highly reactive species are generated that can further combust with excess oxygen. Finally, reaction products from either nPS-NaClO4 composites or nPS alone combusted with only high pressure O2 (400 psig) gas as an oxidizer are captured in a calorimeter bomb. The products in both cases are similar and verified by transmission electron microscopy (TEM) to include nano- to micrometer scale SiOx particles. This work highlights the complex oxidation mechanism of nPS composites and demonstrates the ability to use a solid state reaction to create a secondary gas phase combustion.