Time-resolved thermal lens investigation of glassy dynamics in supercooled liquids: Theory and experiments.

This work reports results on the simultaneous spectroscopy of the specific heat and thermal expansivity of glycerol by making use of a wideband time-resolved thermal lens (TL) technique. An analytical model is presented which describes TL transients in a relaxing system subjected to impulsive laser heating. Experimentally, a set of TL waveforms, from 1 ns to 20 ms, has been recorded for a glycerol sample upon supercooling, from 300 to 200 K. The satisfactory fitting of the TL signals to the model allows the assessment of relaxation strength and relaxation frequency of the two quantities up to sub-100 MHz, extending the specific heat and thermal expansion spectroscopy by nearly three and eight decades, respectively. Fragility values, extracted from the relaxation behavior of the specific heat and the thermal expansion coefficient, are found to be similar, despite a substantial difference in relaxation strength.

Revisiting impulsive stimulated thermal scattering in supercooled liquids: Relaxation of specific heat and thermal expansion.

Impulsive stimulated thermal scattering (ISTS) allows one to access the structural relaxation dynamics in supercooled molecular liquids on a time scale ranging from nanoseconds to milliseconds. Till now, a heuristic semi-empirical model has been commonly adopted to account for the ISTS signals. This model implicitly assumes that the relaxation of specific heat, C, and thermal expansion coefficient, γ, occur on the same time scale and accounts for them via a single stretched exponential. This work proposes two models that assume disentangled relaxations, respectively, based on the Debye and Havriliak-Negami assumptions for the relaxation spectrum and explicitly accounting for the relaxation of C and γ separately in the ISTS response. A theoretical analysis was conducted to test and compare the disentangled relaxation models against the stretched exponential. The former models were applied to rationalize the experimental ISTS signals acquired on supercooled glycerol. This allows us to simultaneously retrieve the frequency-dependent specific heat and thermal expansion up to the sub-100 MHz frequency range and further to compare the fragility and time scale probed by thermal, mechanical, and dielectric susceptibilities.

A Miniature, Fiber-Optic Vibrometer for Measuring Unintended Acoustic Output of Active Hearing Implants during Magnetic Resonance Imaging.

Making use of magnetic resonance imaging (MRI) for diagnostics on patients with implanted medical devices requires caution due to mutual interactions between the device and the electromagnetic fields used by the scanner that can cause a number of adverse events. The presented study offers a novel test method to quantify the risk of unintended output of acoustically stimulating hearing implants. The design and operating principle of an all-optical, MRI safe vibrometer is outlined, followed by an experimental verification of a prototype. Results obtained in an MRI environment indicate that the system can detect peak displacements down to 8 pm for audible frequencies. Feasibility testing was performed with an active middle ear implant that was exposed to several pulse sequences in a 1.5 Tesla MRI environment. Magnetic field induced actuator vibrations, measured during scanning, turned out to be equivalent to estimated sound pressure levels between 25 and 85 dB SPL, depending on the signal frequency. These sound pressure levels are situated well below ambient sound pressure levels generated by the MRI scanning process. The presented case study therefore indicates a limited risk of audible unintended output for the examined hearing implant during MRI.

Visualization of ultrasonic wave field by stroboscopic polarization selective imaging.

A stroboscopic method based on polarization selective imaging is proposed for dynamic visualization of ultrasonic waves propagating in a transparent medium. Multiple independent polarization parametric images were obtained, which enabled quantitative evaluation of the distribution of the ultrasonic pressure in quartz. In addition to the detection of optical phase differences δ in conventional photo-elastic techniques, the azimuthal angle φ and the Stokes parameter S2 of the polarized light are found to be highly sensitive to the wave-induced refraction index distribution, opening a new window on ultrasonic field visualization.

Assessment of short-term exposure to an ultrasonic rodent repellent device.

The objectives of the present study were to investigate the acoustical properties of the very high frequencies and/or ultrasound signals produced by a repellent device and to investigate potential adverse factors as a result of short-term exposure to these signals. Potential adverse effects were evaluated perceptually with 25 young and 25 middle-aged persons, all with normal hearing thresholds, in a quiet room using different outcome measures, including a 15-item survey presented before and immediately after each condition. Spectral analyses showed that, besides emitting frequency modulated sounds in the expected frequency ranges, a faint but audible sound in the 4-5 kHz range was present. On average, a relatively short exposure to the sound produced by a repellent device did not lead to significant adverse effects. Yet, when the signal was perceived, as it was frequently for the younger population at the two lower frequencies settings (12-14 kHz, 25-25 kHz) and with 2 sources emitting, it was considered to be disturbing by several participants. Given the increasing usage of ultrasonic devices as well as the much longer exposure of high frequency and ultrasound in domestic usage, careful consideration and better guidelines are required, especially for those who are most sensitive to sound.

Conformational Changes of a Surface-Tethered Polymer during Radical Growth Probed with Second-Harmonic Generation.

The surface-induced polymerization of a chromophore-functionalized monomer was probed in situ for the first time using a nonlinear optical technique, second-harmonic generation. During the first hours of the polymerization reaction, dramatic changes in the tilt angle of the chromophore-functionalized side groups were observed. Following evaluation of the nonlinear optical data with those obtained from atomic force microscopy and ultraviolet-visible, we conclude that second-harmonic generation efficiently probes the polymerization reaction and the conformational changes of the surface-grafted polymer. With polymerization time, the conformation of the surface-tethered polymer changes from a conformation with the polymer backbone and its side groups flat on the surface, i.e., a "pancake" conformation, to a conformation where the polymer backbone is stretched away combined with tilted side groups or an enlarged tilt angle distribution, i.e., a "brush-type" conformation.

In-situ spectroscopic investigation of ultrasonic assisted unfolding and aggregation of insulin.

It is well-known that fibrillogenesis of proteins can be influenced by diverse external parameters, such as temperature, pressure, agitation or chemical agents. The present preliminary study suggests that ultrasonic excitation at moderate intensities has a significant influence on the unfolding and aggregation behaviour of insulin. Irradiation with an average sound intensity of even as low as 70mW/cm(2) leads to a lowering of the unfolding and aggregation temperature up to 7K. The effect could be explained by an increase of the aggregation kinetics due to ultrasonically induced acoustic micro-streaming in the insulin solution that most probably enhances the aggregation rate. The clear and remarkable effect at relatively low sound intensities offers interesting options for further applications of ultrasound in biophysics and biochemistry. On the other hand, a process that causes a change of kinetics equivalent to 7K also gives a warning signal concerning the safety of those medical ultrasonic devices that work in this intensity range.

Electrical conductivity and glass formation in nitrile-functionalized pyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids: chain length and odd-even effects of the alkyl spacer between the pyrrolidinium ring and the nitrile group.

The electrical conductivity of a series of pyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids, functionalized with a nitrile (cyano) group at the end of an alkyl chain attached to the cation, was studied in the temperature range between 173 K and 393 K. The glass formation of the ionic liquids is influenced by the length of the alkyl spacer separating the nitrile function from the pyrrolidinium ring. The electrical conductivity and the viscosity do not show a monotonic dependence on the alkyl spacer length, but rather an odd-even effect. An explanation for this behavior is given, including the potential energy landscape picture for the glass transition.

Analytical and numerical modeling of nonlinear lamb wave interaction with a breathing crack with low-frequency modulation.

To characterize fatigue crack, an analytical calculation and finite element (FE) simulation of Lamb wave propagating through the region of a breathing crack in a two-dimensional(2D) isotropic plate were studied. Contact surface boundary conditions between the two surfaces of the vertical crack were considered to study contact acoustic nonlinearity (CAN) from the breathing contact crack in conjunction with the modal decomposition method, Fourier transform, and variational principle-based algorithm. Reflection and transmission coefficients in the fundamental frequency and second harmonic frequency were calculated and analyzed quantitatively. Different ratios of incident wave amplitude to crack width were studied to calculate CAN results related to micro-crack width. In addition, a low-frequency (LF) vibration(10 Hz) excitation was introduced to perturb the free surface vertical crack to close, and an interrogating Lamb wave(1 MHz) was used to study crack-related CAN in different conditions for interpreting the modulation mechanism. The contact boundary conditions between two surfaces of vertical crack were set which were dynamically changed due to the low frequency modulation. The clapping effects when the crack closed due to the modulation of the contact boundary conditions between the crack surfaces were studied and analyzed to get the quantitative correlation between CAN and LF modulation. The results obtained from the analytical model were compared with those from the FE simulation, showing good consistency. Knowledge of these effects is essential to correctly gauge the severity of surface cracks in the plate, which can be spotlighted in its application to quantitative evaluation of micro fatigue cracks in structural health monitoring(SHM).

Development and Calibration of a Microfluidic, Chip-Based Sensor System for Monitoring the Physical Properties of Water Samples in Aquacultures.

In this work, we present a compact, bifunctional chip-based sensor setup that measures the temperature and electrical conductivity of water samples, including specimens from rivers and channels, aquaculture, and the Atlantic Ocean. For conductivity measurements, we utilize the impedance amplitude recorded via interdigitated electrode structures at a single triggering frequency. The results are well in line with data obtained using a calibrated reference instrument. The new setup holds for conductivity values spanning almost two orders of magnitude (river versus ocean water) without the need for equivalent circuit modelling. Temperature measurements were performed in four-point geometry with an on-chip platinum RTD (resistance temperature detector) in the temperature range between 2 °C and 40 °C, showing no hysteresis effects between warming and cooling cycles. Although the meander was not shielded against the liquid, the temperature calibration provided equivalent results to low conductive Milli-Q and highly conductive ocean water. The sensor is therefore suitable for inline and online monitoring purposes in recirculating aquaculture systems.

Phase behavior of medium-length hydrophobically associating PEO-PPO multiblock copolymers in aqueous media.

HYPOTHESIS: The micellization of block copolymers of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) is driven by the dehydration of PPO at elevated temperatures. At low concentrations, a viscous solution of isolated micelles is obtained, whereas at higher concentrations, crowding of micelles results in an elastic gel. Alternating PEO-PPO multiblock copolymers are expected to exhibit different phase behavior, with altered phase boundaries and thermodynamics, as compared to PEO-PPO-PEO triblock copolymers (Pluronics®) with equal hydrophobicity, thereby proving the pivotal role of copolymer architecture and molecular weight. EXPERIMENTS: Multiple characterization techniques were used to map the phase behavior as a function of temperature and concentration of PEO-PPO multiblock copolymers (ExpertGel®) in aqueous solution. These techniques include shear rheology, differential and adiabatic scanning calorimetry, isothermal titration calorimetry and light transmittance. The micellar size and topology were studied by dynamic light scattering. FINDINGS: Multiblocks have lower transition temperatures and higher thermodynamic driving forces for micellization as compared to triblocks due to the presence of more than one PPO block per chain. With increasing concentration, the multiblock copolymers in solution gradually evolve into a viscoelastic network formed by soluble bridges in between micellar nodes, whereas hairy triblock micelles jam into liquid crystalline phases resembling an elastic colloidal crystal.

Adaptive polarization photoacoustic computed tomography for biological anisotropic tissue imaging.

Most photoacoustic computed tomography (PACT) systems usually ignore the anisotropy of the tissue absorption coefficient, which will lead to the lack of information in reconstructed images. In this work, the effect is addressed of the possible optical absorption anisotropy of tissue on PACT images. The functional relationship is derived between the photoacoustic response and the polarization angle of the excitation light. An adaptive polarized light photoacoustic imaging (AP-PACT) approach is proposed and shown to make up for the lack of imaging information and achieve optimal image contrast when imaging samples with anisotropic optical absorption, by utilizing the standard deviation of photoacoustic response as the feedback signal in an adaptive data acquisition process. The method is implemented both on phantom and in vitro experiments, which show that AP-PACT can recover anisotropic absorption-related information from reconstructed images and thus significantly improve their quality.

The critical behavior of the refractive index near liquid-liquid critical points.

The nature of the critical behavior in the refractive index n is revisited in the framework of the complete scaling formulation. A comparison is made with the critical behavior of n as derived from the Lorentz-Lorenz equation. Analogue anomalies to those predicted for the dielectric constant ε, namely, a leading |t|(2ß) singularity in the coexistence-curve diameter in the two-phase region and a |t|(1-α) along the critical isopleth in the one phase region, are expected in both cases. However, significant differences as regards the amplitudes of both singularities are obtained from the two approaches. Analysis of some literature data along coexistence in the two-phase region and along the critical isopleth in the one-phase region provide evidence of an intrinsic effect, independent of the density, in the critical anomalies of n. This effect is governed by the shift of the critical temperature with an electric field, which is supposed to take smaller values at optical frequencies than at low frequencies in the Hz to MHz range.

The critical behavior of the dielectric constant in the polar + polar binary liquid mixture nitromethane + 3-pentanol: an unusual sign of its critical amplitude in the one-phase region.

Dielectric constant measurements have been carried out in the one- and two-phase regions near the critical point of the polar + polar binary liquid mixture nitromethane + 3-pentanol. In the two-phase region, evidence for the |t|(2ß) singularity in the coexistence-curve diameter has been detected, thus confirming the novel predictions of complete scaling theory for liquid-liquid criticality. In the one-phase region, an "unusual" negative sign for the amplitude of the |t|(1-α) singularity has been encountered for the first time in an upper critical solution temperature type of binary liquid mixture at atmospheric pressure. Mass density measurements have also been carried out to provide additional information related to such experimental finding, which entails an increase of the critical temperature T(c) under an electric field.

Large heat capacity anomaly near the consolute point of the binary mixture nitromethane and 3-pentanol.

The large critical anomaly in the isobaric heat capacity C(p,x)(T) of the binary mixture nitromethane + 3-pentanol is measured using high-resolution adiabatic scanning calorimetry. The unique features of this technique provided an alternative approach to the study of the critical behavior of C(p,x)(T), providing further C(p,x)(T) related quantities from which valuable information could be extracted. Our data are in full agreement with the predictions of the Modern Theory of Critical Phenomena; specifically, 3D-Ising model values for the critical exponent α and the universal amplitude ratio values of the leading critical amplitudes, as well as for the first correction-to-scaling ones, provide the optimum fits to represent the experimental data. Evidence for the need of higher-order terms, i.e., first correction-to-scaling term, is given. The large value of the coefficient E for the linear temperature dependence of the background obtained is ascribed to a possible contribution of the regular linear background term, of a higher-order asymmetry term, and of the second correction-to-scaling term. Internal consistency of C(p,x)(T) and its related quantities is successfully checked.

Safety of active auditory implants in magnetic resonance imaging.

Magnetic resonance imaging (MRI) has become the gold standard for the diagnosis of many pathologies. Using MRI in patients with auditory implants can however raise concerns due to mutual interactions between the implant and imaging device, resulting in potential patient risks. Several implant manufacturers have been working towards more MRI safe devices. Older devices are however often labelled for more stringent conditions, possibly creating confusion with patients and professionals. With this myriad of different devices that are implanted in patients for lifetimes of at least 20 years, it is crucial that both patients and professionals have a clear understanding of the safety of their devices. This work aims at providing an exhaustive overview on the MRI safety of active auditory implants. The available industry standards that are followed by manufacturers are outlined and an overview of the latest scientific developments focusing on the last five years is provided. In addition, based on the analysis of the adverse events reported to the Food and Drug Administration (FDA) and in literature within the past ten years, a systematic review of the most commonly occurring issues for patients with auditory implants in the MRI environment is provided. Results indicate that despite the release of more MRI conditional active hearing implants on the market, adverse events still occur. An extensive overview is provided on the MRI safety of active auditory implants, aiming to increase the understanding of the topic for healthcare professionals and contribute to safer scanning conditions for patients.

Discrimination of 2D wall textures by passive echolocation for different reflected-to-direct level difference configurations.

In this work, we study people's ability to discriminate between different 2D textures of walls by passive listening to a pre-recorded tongue click in an auralized echolocation scenario. In addition, the impact of artificially enhancing the early reflection magnitude by 6dB and of removing the direct component while equalizing the loudness was investigated. Listening test results for different textures, ranging from a flat wall to a staircase, were assessed using a 2 Alternative-Forced-Choice (2AFC) method, in which 14 sighted, untrained participants were indicating 2 equally perceived stimuli out of 3 presented stimuli. The average performance of the listening subjects to discriminate between different textures was found to be significantly higher for walls at 5m distance, without overlap between the reflected and direct sound, compared to the same walls at 0.8m distance. Enhancing the reflections as well as removing the direct sound were found to be beneficial to differentiate textures. This finding highlights the importance of forward masking in the discrimination process. The overall texture discriminability was found to be larger for the walls reflecting with a higher spectral coloration.

All-optical dynamic analysis of the photothermal and photoacoustic response of a microcantilever by laser Doppler vibrometry.

Light absorption induced thermoelastic and photoacoustic excitation, combined with laser Doppler vibrometry, was utilized to analyze the dynamic mechanical behavior of a microcantilever. The measured frequency response, modal shapes, and acoustic coupling effects were interpreted in the framework of a simple Bernouilli-Euler model and quantitative 3D finite element method (FEM) analysis. Three opto-mechanical generation mechanisms, each initiated by modulated optical absorption and heating, were identified both by an analytical and finite element model. In decreasing order of importance, optically induced cantilever bending is found to be caused by: (i) differences in photoacoustically induced pressure oscillations in the air adjacent to the illuminated and dark side of the cantilever, resulting from heat transfer from the illuminated cantilever to the nearby air, acting as a volume velocity piston, and (ii) thermoelastic stresses accompanying temperature and thermal expansion gradients in the cantilever, (iii) photoacoustically induced pressure oscillations in the air adjacent to the illuminated cantilever holder and frame.

Temperature, concentration, and frequency dependence of the dielectric constant near the critical point of the binary liquid mixture nitrobenzene-tetradecane.

Detailed results are reported for the dielectric constant epsilon as a function of temperature, concentration, and frequency near the upper critical point of the binary liquid mixture nitrobenzene-tetradecane. The data have been analyzed in the context of the recently developed concept of complete scaling. It is shown that the amplitude of the low frequency critical Maxwell-Wagner relaxation (with a relaxation frequency around 10 kHz) along the critical isopleth is consistent with the predictions of a droplet model for the critical fluctuations. The temperature dependence of epsilon in the homogeneous phase can be well described with a combination of a (1-alpha) power law term (with alpha the heat capacity critical exponent) and a linear term in reduced temperature with the Ising value for alpha. For the proper description of the temperature dependence of the difference Deltaepsilon between the two coexisting phases below the critical temperature, it turned out that good fits with the Ising value for the order parameter exponent beta required the addition of a corrections-to-scaling contribution or a linear term in reduced temperature. Good fits to the dielectric diameter epsilon(d) require a (1-alpha) power law term, a 2beta power law term (in the past considered as spurious), and a linear term in reduced temperature, consistent with complete scaling.

Influence of the anion on the electrical conductivity and glass formation of 1-butyl-3-methylimidazolium ionic liquids.

Six ionic liquids based on the 1-butyl-3-methylimidazolium cation have been studied. As anions Cl(-), Br(-), I(-), [NCS](-), [N(CN)(2)](-), and [BF(4)](-) were selected. The electrical conductivities were determined between 173 and 393 K based on impedance measurements in the frequency range from 0.1 to 10(7) Hz. The electrical conductivity increases, whereas the glass transition temperature, the fragility, and the low temperature activation energy decrease with increasing anion size. The results can be understood from the changing anion-cation interaction strength with changing anion size and from the energy landscape interpretation of the glass transition dynamics.