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The maximum size of additively manufactured (AM) components is restricted due to the confined building space of the manufacturing machines. Component separation and subsequent joining can be an effective way of manufacturing larger components using AM processes. For joining of AM components, adhesive bonding provides great potential for not constraining the adherend’s geometry, as long as the adhesive can still be applied to the adhesive surfaces of the adherends. This work investigates the effectiveness and applicability of additively manufactured inner channels to improve the adhesive application. A circular adhesive single lap joint between a laser-based powder bed fusion (PBF-LB) component made of AlSi10Mg and a cold drawn aluminum round bar was considered. The PBF-LB components were designed with varying geometric complexity to implement different adhesive application concepts. Subsequently, the bonded joints were subjected to static tensile tests. The fracture strength of joints where the adhesive was applied by injection into AM inner channels exceeds the fracture strength of joints where the adhesive was injected into geometries manufacturable by subtractive machining, and also exceeds the fracture strength of joints where the adhesive was pre-applied.

Cold-start emissions of the sustainable alternative diesel fuel OME are predominantly NOx, formaldehyde, formic acid and unburned OME. Electrical heating in combination with fuel dosing is an effective method for after-treatment system heating.

Current legislations typically characterize systems of aerosols, such as from vehicle exhaust, primarily by number concentration and size distributions. While potential health threats have a dependence on the particle size, the chemical composition of particles, including the volatile and semi-volatile components adsorbed onto nonvolatile particle cores present at roadside and urban settings, is important in understanding the impact of exhaust particles on health. To date, the only tools suitable for an online in-depth chemical aerosol characterization are aerosol mass spectrometers, which are typically composed of complex and cost intensive instrumentation. We present a new analytical system, which combines a novel inexpensive infrared-radiation-based evaporation system (HELIOS) with a commercially available highly efficient atmospheric ionization source (SICRIT) connected to a rather low-price ion-trap mass spectrometer. Our inexpensive, robust and mobile aerosol characterization HELIOS/SICRIT/Mass Spectrometry system enables highly sensitive chemical analysis of particle-associated volatile substances. We validate the HELIOS/SICRIT/Mass Spectrometry system in laboratory experiments with coated particles generated under controlled conditions, and show that the system is capable of identification of combustion-generated polycyclic aromatic hydrocarbons and relative quantification of individual chemical species adsorbed on particle surfaces. We then employ our system to analyze real-world vehicle engine exhaust aerosol and show through time-resolved measurements with high time resolution (

Hot electrons generated by photoinduced plasmon decay from a plasmonic metal surface can reduce 4-nitrothiophenol (4-NTP) to 4-aminothiophenol (4-ATP). Compared to the reduction with a reducing agent such as sodium borohydride, surface-enhanced Raman scattering (SERS) measurements were performed here to elucidate the complex molecular mechanism of the reduction in the presence of halide ions and hydrogen ions. The SERS measurements were performed using a simply prepared silver plasmonic film (AgPF), which enables monitoring of the reaction under different conditions at a solid-liquid surface and eliminates the need for the use of a reducing agent. As the concentration of H+ and Cl- could be controlled, the observation of the reaction under a systematic set of conditions was possible. Based on the kinetic traces of the intermediates, a reaction mechanism for the 4-NTP to 4-ATP reduction is suggested. Rate constants for the individual reactions are presented that fit the measured kinetic traces, and the role of hydrogen in each reaction step is characterized. This work provides clarification on the molecular transformation directly using protons as the hydrogen source and demonstrates an effective method of applying a simple and low-cost silver surface catalyst for SERS studies. Moreover, the monitoring of Cl--concentration-dependent spectra provides insight into the hot-electron conversion process during the photoreduction and strongly supports the formation of AgCl for the activation of H+.

The photoacoustic signal generated from specific gold nanoparticles increases nonlinearly with respect to fluence. We demonstrate experimentally that this nonlinear behavior can be quenched with a particle coating, and present a theoretical analysis to explain this behavior. This effect has the potential to be developed into a photoacoustic-based biochemical sensor.

Silica-coated gold nanoparticles are commonly employed in biomedical photoacoustic (PA) imaging applications. We investigate theoretically and experimentally the PA signal generation by silica-coated gold nanospheres in water. Our theoretical model considers thermoelastic expansion in the long-pulse illumination regime, and the PA signals are determined based on a semi-analytical solution to the thermal diffusion equations and a finite-difference in time domain (FDTD) solution to the thermoelastic equations. Both the influence of interfacial thermal (Kapitza) resistance at the gold-water boundary and the influence of the silica coating on PA signal generation were investigated. Our results indicate that for the nanosecond pulses commonly employed in PA imaging, Kapitza resistance has a negligible effect on photoacoustic signal generation. Moreover, our model shows that the presence of a silica coating causes a reduction in the PA signal amplitude, with the level of signal reduction increasing with thicker silica coating. Our theoretical predictions are qualitatively consistent with our experimental results, where suspensions of in-house-synthesized and commercially available silica-coated gold nanosphere suspensions were excited with nanosecond-pulsed laser illumination at 532 nm. The PA signal amplitudes from silica-coated nanospheres were lower than the signal amplitudes for uncoated gold nanospheres of the same core gold diameter. The amount of reduction of the experimentally PA signal amplitude due to the silica coating was found to increase with thicker silica coating, in agreement with our theoretical predictions., Comment: 38 pages, 11 figures

The synthesis of nanomaterials through pulsed-laser ablation of a bulk solids can be applied for the generation of reference aerosols for applications in aerosol science, where no reliable source of reference aerosol samples currently exists. To develop aerosol generators based on laser ablation that are capable of reliable aerosol generation with well-defined properties, more data is needed on how the aerosol properties depend on the laser ablation parameters, such as wavelength, power, repetition rate, and surrounding gas. We present an aerosol generation device based on laser ablation from a nanosecond pulsed Nd:YAG laser and report initial data from our systematic study of the effect of ablation parameters on aerosol formation from different metals and graphite. The size and concentration distribution of the resulting laser-ablation-generated aerosols were measured using a scanning mobility particle sizer. The primary nanoparticles formed in the ablation chamber directly as a result of ablation were collected and imaged using scanning electron microscopy and compared to the ensuing aerosols formed after agglomeration of the nanoparticles. We found that the aerosol size and concentration increases with increasing laser irradiance and increasing repetition rate. Different gases were used for the aerosol generation, and our results shed light on how the plasma development and resulting nanoparticle formation depend on the gas environment. Certain metal aerosols formed in a synthetic air environment were larger and more concentrated than in argon and nitrogen. The charge of the aerosols was also monitored using a parallel plate capacitor.

Gold nanoparticles can be used as an exogenous contrast agent for biomedical photoacoustic (PA) imaging. The generation of PA signals in monodispersed gold nanosphere suspensions (diameters 20–150 nm) from pulsed-laser excitation (5 ns pulse width, wavelength 532 nm) was investigated experimentally and compared to signals measured in solutions of a homogeneous molecular absorber. The PA signal amplitude was found to increase linearly with excitation fluence for the homogeneous absorber and the nanospheres up to 80 nm in diameter. By contrast, the signal amplitude was found to increase quadratically with respect to fluence for larger nanospheres. In the linear regime, the PA signal amplitude in gold nanosphere suspensions was found to be on average 26% higher than that in the homogeneous absorber with identical absorption coefficient, which were measured using an integrating sphere. Furthermore, in suspensions with identical absorption coefficient, no dependence of the PA signal amplitude on nanosphere dia...

Real-Time Optoacoustic Monitoring of RF Ablation Introduction Due to lack of reliable imaging contrast from catheter radiofrequency ablation (RFA) lesions, the vast majority of current procedures rely on indirect indicators of ablation activity, resulting in a significant number of arrhythmia reoccurrences after RFA procedures and the need for repeat surgeries. The objective of this work is to develop an accurate method for on-the-fly assessment of the durability and size of lesions formed during RFA procedures. Method and Results Radiofrequency catheter ablation on freshly excised porcine ventricular myocardial tissue was optoacoustically monitored by means of pulsed-laser illumination in the near-infrared spectrum. Lesion formation during ablation was captured at a rate of 10 Hz with a 256-detector optoacoustic imaging probe. Postablated samples were imaged using multispectral excitation in the wavelength range 740–860 nm to determine the lesion contrast spectrum. Tomographic reconstruction was performed to generate 3-dimensional images of the lesions, which were compared to photographs depicting the final ablated tissue samples. Video-rate 3-dimensional tomographic reconstructions depict formation of the lesion with high contrast and spatial resolution. The size and geometry of the lesion was shown to be in excellent agreement with the histological examinations. The wavelength dependence of the lesion contrast shows a contrast peak near 780 nm. Conclusion Deep-tissue 3-dimensional monitoring of RFA lesion generation in real time was demonstrated for the first time in this work. The results suggest the potential of optoacoustic monitoring for providing critical feedback on lesion position and size during radiofrequency catheter ablation, improving safety and efficacy of these treatments.

Lack of sensory feedback during laser surgery prevents surgeons from discerning the exact location of the incision, which increases duration and complexity of the treatment. In this study we demonstrate a new method for monitoring of laser ablation procedures. Real-time tracking of the exact three dimensional (3D) lesion profile is accomplished by detection of shock waves emanating from the ablation spot and subsequent reconstruction of the incision location using time-of-flight data obtained from multiple acoustic detectors. Here, incisions of up to 9 mm in depth, created by pulsed laser ablation of fresh bovine tissue samples, were successfully monitored in real time. It was further observed that, by utilizing as little as 12 detection elements, the incision profile can be characterized with accuracy below 0.5 mm in all three dimensions and in good agreement with histological examinations. The proposed method holds therefore promise for delivering high precision real-time feedback during laser surgeries.

We report a constrained-reaction-volume strategy for conducting kinetics experiments behind reflected shock waves, achieved in the present work by staged filling in a shock tube. Using hydrogen–oxygen ignition experiments as an example, we demonstrate that this strategy eliminates the possibility of non-localized (remote) ignition in shock tubes. Furthermore, we show that this same strategy can also effectively eliminate or minimize pressure changes due to combustion heat release, thereby enabling quantitative modeling of the kinetics throughout the combustion event using a simple assumption of specified pressure and enthalpy. We measure temperature and OH radical time-histories during ethylene–oxygen combustion behind reflected shock waves in a constrained reaction volume and verify that the results can be accurately modeled using a detailed mechanism and a specified pressure and enthalpy constraint.

Optoacoustic techniques rely on ultrasound transmission between optical absorbers within tissues and the measurement location. Much like in echography, commonly used piezoelectric transducers require either direct contact with the tissue or through a liquid coupling medium. The contact nature of this detection approach then represents a disadvantage of standard optoacoustic systems with respect to other imaging modalities (including optical techniques) in applications where non-contact imaging is needed, e.g. in open surgeries or when burns or other lesions are present in the skin. Herein, non-contact optoacoustic imaging using raster-scanning of a spherically-focused piezoelectric air-coupled ultrasound transducer is demonstrated. When employing laser fluence levels not exceeding the maximal permissible human exposure, it is shown possible to attain detectable signals from objects as small as 1 mm having absorption properties representative of blood at near-infrared wavelengths with a relatively low number of averages. Optoacoustic images from vessel-mimicking tubes embedded in an agar phantom are further showcased. The initial results indicate that the air-coupled ultrasound detection approach can be potentially made suitable for non-contact biomedical imaging with optoacoustics.

The rate constant for the overall reaction OH + 1-butanol → products was determined in the temperature range 900 to 1200 K from measurements of OH concentration time histories in reflected shock wave experiments of tert-butyl hydroperoxide (TBHP) as a fast source of OH radicals with 1-butanol in excess. Narrow-linewidth laser absorption was employed for the quantitative OH concentration measurement. A detailed kinetic mechanism was constructed that includes updated rate constants for 1-butanol and TBHP kinetics that influence the near-first-order OH concentration decay under the present experimental conditions, and this mechanism was used to facilitate the rate constant determination. The current work improves upon previous experimental studies of the title rate constant by utilizing a rigorously generated kinetic model to describe secondary reactions. Additionally, the current work extends the temperature range of experimental data in the literature for the title reaction under combustion-relevant conditions, presenting the first measurements from 900 to 1000 K. Over the entire temperature range studied, the overall rate constant can be expressed in Arrhenius form as 3.24 × 10(-10) exp(-2505/T [K]) cm(3) molecule(-1) s(-1). The influence of secondary reactions on the overall OH decay rate is discussed, and a detailed uncertainty analysis is performed yielding an overall uncertainty in the measured rate constant of ±20% at 1197 K and ±23% at 925 K. The results are compared with previous experimental and theoretical studies on the rate constant for the title reaction and reasonable agreement is found when the earlier experimental data were reinterpreted.

Rate constants for the overall reactions of OH with n-pentane, n-heptane, and n-nonane were measured in shock tube experiments behind reflected shock waves. Narrow-linewidth laser absorption by OH at 306.7 nm was used in pseudo first-order experiments with temperatures between 869 to 1364 K. tert-Butyl hydroperoxide (TBHP) was used as the OH precursor. Experiments were also performed to study the kinetics of the TBHP decomposition and resulting product chemistry, and an accurate mechanism describing OH precursor chemistry effects was developed to model OH concentration time-history in the n-alkane + OH experiments. The experimental results for the n-alkane + OH rate constant measurements can be expressed as rate constants in Arrhenius form as k n-pentane + OH = 2.10 × 10-10 exp(-2038/T[K]) (869–1364 K), k n-heptane + OH = 2.43 × 10-10 exp(-1804/T[K]) (869–1364 K), k n-nonane + OH = 3.17 × 10-10 exp(-1801/T[K]) (884–1352 K), each in units of cm3 molecule-1 s-1. The present rate constants measured for OH with n-pentane and n-heptane show agreement within 20% with recent work by Sivaramakrishnan and Michael [J. Phys. Chem. A, 113 (2009) 5047]. The measurements of the rate constant for n-nonane + OH presented here represent the first in the literature to depict the temperature dependence of the rate constant above 800 K. The measurements of each n-alkane + OH rate constant studied were compared with two models in the literature used to estimate the rate constants of n-alkane + OH reactions. The Structure-Activity Relationship of Kwok and Atkinson [Atmos. Environ., 29 (1995) 1685] shows the best agreement with the current data for all three n-alkanes over the entire temperature range studied, demonstrating that this model is capable of predicting the overall rate constants for reactions of OH with n-pentane, n-heptane, and n-nonane for temperatures up to 1364 K.

Non-ideal shock tube facility effects, such as incident shock wave attenuation, can cause variations in the pressure histories seen in reflected shock wave experiments. These variations can be reduced, and in some cases eliminated, by the use of driver inserts. Driver inserts, when designed properly, act as sources of expansion waves which can counteract or compensate for gradual increases in reflected shock pressure profiles. An algorithm for the design of these inserts is provided, and example pressure measurements are presented that demonstrate the success of this approach. When these driver inserts are employed, near- ideal, constant-volume performance in reflected shock wave experiments can be achieved, even at long test times. This near-ideal behavior simplifies the interpretation of shock tube chemical kinetics experiments, particularly in experiments which are highly sensitive to temperature and pressure changes, such as measurements of ignition delay time of exothermic reactions.

Recent literature has indicated that experimental shock tube ignition delay times for hydrogen combustion at low-temperature conditions may deviate significantly from those predicted by current detailed kinetic models. The source of this difference is uncertain. In the current study, the effects of shock tube facility-dependent gasdynamics and localized pre-ignition energy release are explored by measuring and simulating hydrogen–oxygen ignition delay times. Shock tube hydrogen–oxygen ignition delay time data were taken behind reflected shock waves at temperatures between 908 to 1118 K and pressures between 3.0 and 3.7 atm for two test mixtures: 4% H2, 2% O2, balance Ar, and 15% H2, 18% O2, balance Ar. The experimental ignition delay times at temperatures below 980 K are found to be shorter than those predicted by current mechanisms when the normal idealized constant volume (V) and internal energy (E) assumptions are employed. However, if non-ideal effects associated with facility performance and energy release are included in the modeling (using CHEMSHOCK, a new model which couples the experimental pressure trace with the constant V, E assumptions), the predicted ignition times more closely follow the experimental data. Applying the new CHEMSHOCK model to current experimental data allows refinement of the reaction rate for H + O2 + Ar ↔ HO2 + Ar, a key reaction in determining the hydrogen–oxygen ignition delay time in the low-temperature region.

Non-contact optoacoustic imaging employing raster-scanning of a spherically focused air-coupled ultrasound transducer is showcased herein. Optoacoustic excitation with laser fluence within the maximal permissible human exposure limits in the visible and near-infrared spectra is applied to objects with characteristic dimensions smaller than 1 mm and absorption properties representative of the whole blood at near-infrared wavelengths, and these signals are shown to be detectable without contact to the sample using an air-coupled transducer with reasonable signal averaging. Optoacoustic images of vessel-mimicking tubes embedded in an agar phantom captured with this non-contact sensing technique are also showcased. These initial results indicate that an air-coupled ultrasound detection approach can be suitable for non-contact biomedical imaging with optoacoustics.

One of the current problems facing kinetics modeling of combustion processes in shock tubes is the need for a simple, well-defined gasdynamics model that can be used to describe the time-dependent reflected test gas conditions throughout energetic ignition events. The near-constant-pressure or near-constant-volume assumption that may be valid before ignition is clearly violated behind reflected shock waves in conventional shock tubes when there is large energy release. In these cases, accurate modeling, both gasdynamic and chemical, throughout the ignition event is effectively impossible without having to resort to multi-dimensional computation schemes.

The overall rate constant for the reaction ethanol + OH → products was determined experimentally from 900 to 1270 K behind reflected shock waves. Ethan(18)ol was utilized for these measurements in order to avoid the recycling of OH radicals following H-atom abstraction at the β-site of ethanol. Similar experiments were also performed with unlabeled ethan(16)ol in order to infer the rate constant that excludes reactivity at the β-site. The two data sets were used to directly infer the branching ratio for the reaction at the β-site. Experimental data in the current study and in previous low-temperature studies for the overall rate constant are best fit by the expression koverall = 5.07 × 10(5) T[K](2.31) exp(608/T[K]) cm(3) mol(-1) s(-1), valid from 300 to 1300 K. Measurements indicate that the branching ratio of the β-site is between 20 and 25% at the conditions studied. Pseudo-first-order reaction conditions were generated using tert-butylhydroperoxide (TBHP) as a fast source of (16)OH with ethanol in excess. (16)OH mole fraction time-histories were measured using narrow-line width laser absorption near 307 nm. Measurements were performed at the linecenter of the R22(5.5) transition in the A-X(0,0) band of (16)OH that does not overlap with any absorption features of (18)OH, thus producing a measurement of the (16)OH mole fraction that is insensitive to the presence of (18)OH.

Lack of sensory feedback during laser surgery prevents surgeons from discerning the exact location of the incision, which increases duration and complexity of the treatment. In this study we demonstrate a new method for monitoring of laser ablation procedures. Real-time tracking of the exact three dimensional (3D) lesion profile is accomplished by detection of shock waves emanating from the ablation spot and subsequent reconstruction of the incision location using time-of-flight data obtained from multiple acoustic detectors. Here, incisions of up to 9 mm in depth, created by pulsed laser ablation of fresh bovine tissue samples, were successfully monitored in real time. It was further observed that, by utilizing as little as 12 detection elements, the incision profile can be characterized with accuracy below 0.5 mm in all three dimensions and in good agreement with histological examinations. The proposed method holds therefore promise for delivering high precision real-time feedback during laser surgeries.

This work presents the first direct experimental study of the rate constant for the reaction of OH with iso-butanol (2-methyl-1-propanol) at temperatures from 907 to 1147 K at near-atmospheric pressures. OH time-histories were measured behind reflected shock waves using a narrow-linewidth laser absorption method during reactions of dilute mixtures of tert-butylhydroperoxide (as a fast source of OH) with iso-butanol in excess. The title reaction's overall rate constant (OH + iso-butanol →(k(overall)) all products) minus the rate constant for the β-radical-producing channel (OH + iso-butanol →(k(β)) 1-hydroxy-2-methyl-prop-2-yl radical + H(2)O) was determined from the pseudo-first-order rate of OH decay. A two-parameter Arrhenius fit of the experimentally determined rate constant in the current temperature range yields the expression (k(overall) - k(β)) = 1.84 × 10(-10) exp(-2350/T[K]) cm(3) molecule(-1) s(-1). A recommendation for the overall rate constant, including k(β), is made, and comparisons of the results to rate constant recommendations from the literature are discussed.