Retention Forces for Drops on Microstructured Superhydrophobic Surfaces.

Accurate models of retention forces between drops and superhydrophobic (SH) surfaces are required to predict drop dynamics on the surface. This retention force is, in turn, useful in modeling heat transfer rates for dropwise condensation on a SH surface. Drop contact angle distribution and base area on SH surfaces are essential factors for predicting retention forces. The present work measures the contact angle distribution and base area shapes of various drop sizes over a wide range of solid fraction for inclined microstructured SH surfaces at the point of drop departure. Base area shape was found to be well approximated using two ellipses with different aspect ratios, and the contact angle distribution was found to be best fit by a sigmoid function. At an incline near the roll-off angle, drop base area for surfaces with solid fraction close to 1 and close to 0 were found to be nearly circular, whereas the base area of drops on surfaces with an intermediate solid fraction deviated from circular behavior. In this work, maximum advancing and minimum receding contact angles were found as a function of solid fraction and used to calculate retention forces. Contact angle distribution and base area shapes are then used to calculate retention forces between drops and SH surfaces. These calculations are compared with the component of measured drop weight acting parallel to the plane on a tilted surface for validation. Previous retention force studies that investigate base area shape and contact angle distribution for smooth surfaces are not applicable for microstructured SH surfaces. The work shows that using a sigmoid contact angle distribution and modified base area shape yields retention forces that are on average 50% better than previously reported methods. Retention forces for smooth and SH surfaces calculated in this study were used to suggest retention force factor values for varying solid fraction surfaces.

Comparison of the Dynamic Thermal Gradient to Temperature-Programmed Conditions in Gas Chromatography Using a Stochastic Transport Model.

This paper compares dynamic (i.e., temporally changing) thermal gradient gas chromatography (GC) to temperature-programmed GC using a previously published stochastic transport model to simulate peak characteristics for the separation of C12-C40 hydrocarbons. All comparisons are made using chromatographic conditions that give approximately equal analyte retention times (tR). As shown previously, a static thermal gradient does not improve resolution (Rs) equally for all analytes, which highlights the need for a dynamic thermal gradient. An optimal dynamic thermal gradient should result in constant analyte velocities at any instant in time for those analytes that are actively being separated (i.e., analytes that have low retention factors). The average separation temperature for each analyte is used to determine the thermal gradient profile at different times in the temperature ramp. Because many of the analytes require a similar thermal gradient profile when actively being separated, the thermal gradient profile in this study was held fixed; however, the temperature of the entire thermal gradient was raised over time. From the simulations performed in this study, optimized dynamic thermal gradient conditions are shown to improve Rs by up to 13% over comparative temperature-programmed conditions, even with a perfect injection (i.e., zero injection bandwidth). In the dynamic thermal gradient simulations, all analytes showed improvements in Rs along with slightly shorter tR values compared to simulations for traditional temperature-programmed conditions.

Comparison of Static Thermal Gradient to Isothermal Conditions in Gas Chromatography Using a Stochastic Transport Model.

This paper compares static (i.e., temporally unchanging) thermal gradient gas chromatography (GC) to isothermal GC using a stochastic transport model to simulate peak characteristics for the separation of C12-C14 hydrocarbons resulting from variations in injection bandwidth. All comparisons are made using chromatographic conditions that give approximately equal analyte retention times so that the resolution and number of theoretical plates can be clearly compared between simulations. Simulations show that resolution can be significantly improved using a linear thermal gradient along the entire column length. This is mainly achieved by partially compensating for loss in resolution from the increase in mobile phase velocity, which approximates an ideal, basic separation. The slope of the linear thermal gradient required to maximize resolution is a function of the retention parameters, which are specific to each analyte pair; a single static, thermal gradient will not affect all analytes equally. A static, non-linear thermal gradient that creates constant analyte velocities at all column locations provides the largest observed gains in resolution. From the simulations performed in this study, optimized linear thermal gradient conditions are shown to improve the resolution by as much as 8.8% over comparative isothermal conditions, even with a perfect injection (i.e., zero initial bandwidth).

Simulating Capillary Gas Chromatographic Separations including Thermal Gradient Conditions.

This article presents a method of simulating molecular transport in capillary gas chromatography (GC) applicable to isothermal, temperature-programmed, and thermal gradient conditions. The approach accounts for parameter differences that can occur across an analyte band including pressure, mobile phase velocity, temperature, and retention factor. The model was validated experimentally using a GC column comprised of microchannels in a stainless-steel plate capable of isothermal, temperature-programmed, and thermal gradient GC separations. The parameters governing retention and dispersion in the transport model were fitted with 12 experimental isothermal separations. The transport model was validated with experimental data for three analytes using four temperature-programmed and three thermal gradient GC separations. The simulated peaks (elution time and dispersion) give reasonable predictions of observed separations. The magnitudes of the maximum error between simulated peak elution time and experiment were 2.6 and 4.2% for temperature-programmed and thermal gradient GC, respectively. The magnitudes of the maximum error between the simulated peak width and experiment were 15.4 and 5.8% for temperature-programmed and thermal gradient GC, respectively. These relatively low errors give confidence that the model reflects the behavior of the transport processes and provides meaningful predictions for GC separations. This transport model allows for an evaluation of analyte separation characteristics of the analyte band at any position along the length of the GC column in addition to peak characteristics at the column exit. The transport model enables investigation of column conditions that influence separation behavior and opens exploration of optimal column design and heating conditions.

Simulation of Drop-Size Distribution During Dropwise and Jumping Drop Condensation on a Vertical Surface: Implications for Heat Transfer Modeling.

Accurate models for condensation heat transfer are necessary to improve condenser design. Drop-size distribution is an important aspect of heat transfer modeling that is difficult to measure for small drop sizes. The present work uses a numerical simulation of condensation which incorporates the possibility of coalescence and coalescence-induced jumping over a range of drop sizes. Results of the simulation are compared with previous theoretical models and the impact of the assumptions used in those models is explored. In particular, previous drop-size distribution models may predict heat transfer rates less accurately for high contact angles and for coalescence-induced jumping since coalescence occurs over a range of drop sizes and does not always result in departure. The influence of various input parameters (nucleation site distribution approach, nucleation site density, contact angle, maximum drop size, heat transfer modeling to individual drops, and minimum jumping size) on the drop-size distribution and overall heat transfer rate is explored. Assignment of the nucleation site spatial distribution and heat transfer model affect both the drop-size distribution and predicted overall heat transfer rate. Results from the simulation suggest that, when the contact angle is large (as on superhydrophobic surfaces) and no coalescence-induced jumping occurs, the heat transfer may not be as sensitive to the maximum drop-size as previously supposed. Furthermore, this work suggests that when coalescence-induced jumping occurs, reducing the maximum drop size may not always increase heat transfer since drops similar in size to those removed by coalescence-induced jumping can contribute significantly to the overall heat transfer rate.

Stainless-Steel Column for Robust, High-Temperature Microchip Gas Chromatography.

This paper reports the first results of a robust, high-performance, stainless-steel microchip gas-chromatography (GC) column that is capable of analyzing complex real-world mixtures as well as operating at very high temperatures. Using a serpentine design, a 10 m column with an approximately semicircular cross-section with a 52 µm hydraulic diameter ( Dh) was produced in a 17 × 6.3 × 0.1 cm rectangular steel chip. The channels were produced using a multilayer-chemical-etch and diffusion-bonding process, and metal nuts were brazed onto the inlet and outlet ports allowing for column interfacing with ferrules and fused silica capillary tubing. After deactivating the metal surface, channels were statically coated with a ≈0.1 µm layer of 5% phenyl-1% vinyl-methylpolysiloxane (SE-54) stationary phase and cross-linked with dicumyl peroxide. By using n-tridecane ( n-C13) as a test analyte with a retention factor ( k) of 5, a total of 44 500 plates (≈4500 plates per meter) was obtained isothermally at 120 °C. The column was thermally stable to at least 350 °C, and rapid temperature programming (35 °C/min) was demonstrated for the boiling-point range from n-C5 to n-C44 (ASTM D2887 simulated-distillation standard). The column was also tested for separation of two complex mixtures: gasoline headspace and kerosene. These initial experiments demonstrate that the planar stainless-steel column with proper interfacing can be a viable alternative platform for portable, robust microchip GC that is capable of high-temperature operation for low-volatility-compound analysis.

Electrochemical Glucose Sensors Enhanced by Methyl Viologen and Vertically Aligned Carbon Nanotube Channels.

Freestanding, vertically aligned carbon nanotubes (VACNTs) were patterned into 16 µm diameter microchannel arrays for flow-through electrochemical glucose sensing. Non-enzymatic sensing of glucose was achieved by the chemical reaction of glucose with methyl viologen (MV) at an elevated temperature and pH (0.1 M NaOH), followed by the electrochemical reaction of reduced-MV with the VACNT surface. The MV sensor required no functionalization (including no metal) and was able to produce on average 3.4 electrons per glucose molecule. The current density of the MV sensor was linear with both flow rate and glucose concentration. Challenges with interference chemicals were mitigated by operating at a low potential of -0.2 V vs Ag/AgCl. As a comparison, enzymatic VACNT sensors with platinum nano-urchins were functionalized with glucose oxidase by covalent binding (1-ethyl-3-(-3-dimethylaminopropyl)carbodiimide/ N-hydroxysuccinimide) or by polymer entrapment [poly(3,4-ethylene-dioxythiophene)] and operated in phosphate buffered saline. With normalization by the overall cross-sectional area of the flow (0.713 cm2), the sensitivity of the MV, enzyme-in-solution, and covalent sensors were 45.93, 18.77, and 1.815 mA cm-2 mM-1, respectively. Corresponding limits of detection were 100, 194, and 311 nM glucose. The linear sensing ranges for the sensors were 250 nM to 200 µM glucose for the MV sensor, 500 nM to 200 µM glucose for the enzyme-in-solution sensor, and 1 µM to 6 mM glucose for the covalent sensor. The flow cell and sensor cross-sectional area were scaled down (0.020 cm2) to enable detection from 200 µL of glucose with MV by flow injection analysis. The sensitivity of the small MV sensor was 5.002 mA cm-2 mM-1, with a limit of detection of 360 nM glucose and a linear range up to at least 150 µM glucose. The small MV sensor has the potential to measure glucose levels found in 200 µL of saliva.

CIP2A immunosensor comprised of vertically-aligned carbon nanotube interdigitated electrodes towards point-of-care oral cancer screening.

Vertically aligned carbon nanotube array (VANTA) coatings have recently garnered significant attention due in part to their unique material properties including light absorption, chemical inertness, and electrical conductivity. Herein we report the first use of VANTAs grown via chemical vapor deposition in a 2D interdigitated electrode (IDE) footprint with a high height-to-width aspect ratio (3:1 or 75:25 µm). The VANTA-IDEs were functionalized with an antibody (Ab) specific to the human cancerous inhibitor PP2A (CIP2A)-an oncoprotein that is associated with a variety of malignancies such as oral, breast, and multiple myeloma cancers. The resultant label-free immunosensor was capable of detecting CIP2A across a wide linear sensing range (1-100 pg/mL) with a detection limit of 0.24 pg/mL within saliva supernatant-a range that is more sensitive than the corresponding CIP2A enzyme linked immunosorbent assay (ELISA). These results help pave the way for rapid cancer screening tests at the point-of-care (POC) such as for the early-stage diagnosis of oral cancer at a dentist's office.

Extending the upper temperature range of gas chromatography with all-silicon microchip columns using a heater/clamp assembly.

Miniaturization of gas chromatography (GC) instrumentation is of interest because it addresses current and future issues relating to compactness, portability and field application. While incremental advancements continue to be reported in GC with columns fabricated in microchips (referred to in this paper as "microchip columns"), the current performance is far from acceptable. This lower performance compared to conventional GC is due to factors such as pooling of the stationary phase in corners of non-cylindrical channels, adsorption of sensitive compounds on incompletely deactivated surfaces, shorter column lengths and less than optimum interfacing to injector and detector. In this work, a GC system utilizing microchip columns was developed that solves the latter challenge, i.e., microchip interfacing to injector and detector. A microchip compression clamp was constructed to heat the microchip (i.e., primary heater), and seal the injector and detector fused silica interface tubing to the inlet and outlet ports of the microchip channels with minimum extra-column dead volume. This clamp allowed occasional operation up to 375°C and routine operation up to 300°C. The compression clamp was constructed of a low expansion alloy, Kovar™, to minimize leaking due to thermal expansion mismatch at the interface during repeated thermal cycling, and it was tested over several months for more than one hundred injections without forming leaks. A 5.9m long microcolumn with rectangular cross section of 158µm×80µm, which approximately matches a 100µm i.d. cylindrical fused silica column, was fabricated in a silicon wafer using deep reactive ion etching (DRIE) and high temperature fusion bonding; finally, the channel was coated statically with a 1% vinyl, 5% phenyl, 94% methylpolysiloxane stationary phase. High temperature separations of C10-C40 n-alkanes and a commercial diesel sample were demonstrated using the system under both temperature programmed GC (TPGC) and thermal gradient GC (TGGC) conditions. TGGC analysis of a complex essential oil sample was also demonstrated. Addition of a secondary heater and polyimide insulation proved to be helpful in achieving the desired elution temperature without having to raise the primary heater temperature above 300°C for high boiling point compounds.

High Aspect Ratio Carbon Nanotube Membranes Decorated with Pt Nanoparticle Urchins for Micro Underwater Vehicle Propulsion via H2O2 Decomposition.

The utility of unmanned micro underwater vehicles (MUVs) is paramount for exploring confined spaces, but their spatial agility is often impaired when maneuvers require burst-propulsion. Herein we develop high-aspect ratio (150:1), multiwalled carbon nanotube microarray membranes (CNT-MMs) for propulsive, MUV thrust generation by the decomposition of hydrogen peroxide (H2O2). The CNT-MMs are grown via chemical vapor deposition with diamond shaped pores (nominal diagonal dimensions of 4.5 × 9.0 µm) and subsequently decorated with urchin-like, platinum (Pt) nanoparticles via a facile, electroless, chemical deposition process. The Pt-CNT-MMs display robust, high catalytic ability with an effective activation energy of 26.96 kJ mol(-1) capable of producing a thrust of 0.209 ± 0.049 N from 50% [w/w] H2O2 decomposition within a compact reaction chamber of eight Pt-CNT-MMs in series.

Note: Thermal analog to atomic force microscopy force-displacement measurements for nanoscale interfacial contact resistance.

Thermal diffusion measurements on polymethylmethacrylate-coated Si substrates using heated atomic force microscopy tips were performed to determine the contact resistance between an organic thin film and Si. The measurement methodology presented demonstrates how the thermal contrast signal obtained during a force-displacement ramp is used to quantify the resistance to heat transfer through an internal interface. The results also delineate the interrogation thickness beyond which thermal diffusion in the organic thin film is not affected appreciably by the underlying substrate.