1H NMR study of proton dynamics in (NH4)3H(SO4)2

Proton dynamics in (NH₄)₃H(SO₄)₂ has been studied by means of ¹H solid-state NMR. The ¹H magic-angle-spinning (MAS) NMR spectra were traced at room temperature (RT) and at Larmor frequency of 400.13 MHz. ¹H static NMR spectra were measured at 200.13 MHz in the range of 135–490 K. ¹H spin-lattice relaxation times, T₁, were measured at 200.13 and 19.65 MHz in the ranges of 135–490 and 153–456 K, respectively. The ¹H chemical shift for the acidic proton (14.7 ppm) indicates strong hydrogen bonds. In phase III, NH₄⁺ reorientation takes place; one type of NH₄⁺ ions reorients with an activation energy (E_a) of 14 kJ mol^− 1 and the inverse of a frequency factor (τ₀) of 0.85 × 10^− 14 s. In phase II, a very fast local and anisotropic motion of the acidic protons takes place. NH₄⁺ ions start to diffuse translationally, and no proton exchange is observed between NH₄⁺ ions and the acidic protons. In phase I, both NH₄⁺ ions and the acidic protons diffuse translationally. The acidic protons diffuse with parameters of E_a = 27 kJ mol^− 1 and τ₀ = 4.2 × 10^− 13 s. The translational diffusion of the acidic protons is responsible for the macroscopic proton conductivity, as the NH₄⁺ translational diffusion is slow and proton exchange between NH₄⁺ ions and the acidic protons is negligible.     

Production of particulates from transducer erosion: Implications on food safety

The formation of metallic particulates from erosion was investigated by running a series of transducers at various frequencies in water. Two low frequency transducer sonotrodes were run for 7.5 h at 18 kHz and 20 kHz. Three high frequency plates operating at megasonic frequencies of 0.4 MHz, 1 MHz, and 2 MHz were run over a 7 days period. Electrical conductivity and pH of the solution were measured before and after each run. A portion of the non-sonicated and treated water was partially evaporated to achieve an 80-fold concentration of particles and then sieved through nano-filters of 0.1 μm, 0.05 μm, and 0.01 μm. An aliquot of the evaporated liquid was also completely dried on strips of carbon tape to determine the presence of finer particles post sieving. An aliquot was analyzed for detection of 11 trace elements by Inductively Coupled Plasma Mass Spectroscopy (ICPMS). The filters and carbon tapes were analyzed by FE-SEM imaging to track the presence of metals by EDS (Energy Dispersive Spectroscopy) and measure the particle size and approximate composition of individual particles detected. Light microscopy visualization was used to calculate the area occupied by the particles present in each filter and high resolution photography was used for visualization of sonotrode surfaces. The roughness of all transducers before and after sonication was tested through profilometry. No evidence of formation of nano-particles was found at any tested frequency. High amounts of metallic micron-sized particles at 18 kHz and 20 kHz formed within a day, while after 7 day runs only a few metallic micro particles were detected above 0.4 MHz. Erosion was corroborated by an increase in roughness in the 20 kHz tip after ultrasound. The elemental analysis showed that metal leach occurred but values remained below accepted drinking water limits, even after excessively long exposure to ultrasound. With the proviso that the particles measured here were only characterized in two dimensions and could be nanoparticulate in terms of the third dimension, this research suggests that there are no serious health implications resulting from the formation of nanoparticles under the evaluation conditions. Therefore, high frequency transducer plates can be safely operated in direct contact with foods. However, due to significant production of metallic micro-particulates, redesign of lower frequency sonotrodes and reaction chambers is advised to enable operation in various food processing direct-contact applications.     

Ultrasound pressure distributions generated by high frequency transducers in large reactors

The performance of an ultrasound reactor chamber relies on the sound pressure level achieved throughout the system. The active volume of a high frequency ultrasound chamber can be determined by the sound pressure penetration and distribution provided by the transducers. This work evaluated the sound pressure levels and uniformity achieved in water by selected commercial scale high frequency plate transducers without and with reflector plates. Sound pressure produced by ultrasonic plate transducers vertically operating at frequencies of 400 kHz (120 W) and 2 MHz (128 W) was characterized with hydrophones in a 2 m long chamber and their effective operating distance across the chamber’s vertical cross section was determined. The 2 MHz transducer produced the highest pressure amplitude near the transducer surface, with a sharp decline of approximately 40% of the sound pressure occurring in the range between 55 and 155 mm from the transducer. The placement of a reflector plate 500 mm from the surface of the transducer was shown to improve the sound pressure uniformity of 2 MHz ultrasound. Ultrasound at 400 kHz was found to penetrate the fluid up to 2 m without significant losses. Furthermore, 400 kHz ultrasound generated a more uniform sound pressure distribution regardless of the presence or absence of a reflector plate. The choice of the transducer distance to the opposite reactor wall therefore depends on the transducer plate frequency selected. Based on pressure measurements in water, large scale 400 kHz reactor designs can consider larger transducer distance to opposite wall and larger active cross-section, and therefore can reach higher volumes than when using 2 MHz transducer plates.     

Frequency agile antennas based on aluminum nitride ceramics

In this paper, the frequency agile antennas made using aluminum nitride ceramic substrate are investigated theoretically and experimentally. The aluminum nitride ceramic substrates are prepared by pressing and sintering aluminum nitride powders. The operating frequency of antenna is designed to operate at 2.45 and 5.80 GHz. The shape of the patch attaching on the aluminum nitride substrate was rectangular form, and the dc bias is applied between patch and ground plane. This simple technique is used to implement electronically tunable antenna. Deformation of the antenna due to the applied dc bias is obtained as the computation of thickness and extension strains. The simulated frequency shifts at 2.45 and 5.80 GHz, are 7.42 and 7.70 MHz, and the experimentally measured frequency shifts at the same frequencies are 7.50 and 8.50 MHz, respectively. The theoretically simulated results show an average error of less than 4.45% compared with the experimental results.     

Design parameters of stainless steel plates for maximizing high frequency ultrasound wave transmission

This work validated, in a higher frequency range, the theoretical predictions made by Boyle around 1930, which state that the optimal transmission of sound pressure through a metal plate occurs when the plate thickness equals a multiple of half the wavelength of the sound wave. Several reactor design parameters influencing the transmission of high frequency ultrasonic waves through a stainless steel plate were examined. The transmission properties of steel plates of various thicknesses (1–7 mm) were studied for frequencies ranging from 400 kHz to 2 MHz and at different distances between plates and transducers. It was shown that transmission of sound pressure through a steel plate showed high dependence of the thickness of the plate to the frequency of the sound wave (thickness ratio). Maximum sound pressure transmission of ∼60% of the incident pressure was observed when the ratio of the plate thickness to the applied frequency was a multiple of a half wavelength (2 MHz, 6 mm stainless steel plate). In contrast, minimal sound pressure transmission (∼10–20%) was measured for thickness ratios that were not a multiple of a half wavelength. Furthermore, the attenuation of the sound pressure in the transmission region was also investigated. As expected, it was confirmed that higher frequencies have more pronounced sound pressure attenuation than lower frequencies. The spatial distribution of the sound pressure transmitted through the plate characterized by sonochemiluminescence measurements using luminol emission, supports the validity of the pressure measurements in this study.     

Creaming enhancement in a liter scale ultrasonic reactor at selected transducer configurations and frequencies

Recent research has shown that high frequency ultrasound (0.4–3 MHz), can enhance milkfat separation in small scale systems able to treat only a few milliliters of sample. In this work, the effect of ultrasonic standing waves on milkfat creaming was studied in a 6 L reactor and the influence of different frequencies and transducer configurations in direct contact with the fluid was investigated. A recombined coarse milk emulsion with fat globules stained with oil-red-O dye was selected for the separation trials. Runs were performed with one or two transducers placed in vertical (parallel or perpendicular) and horizontal positions (at the reactor base) at 0.4, 1 and/or 2 MHz (specific energy 8.5 ± 0.6 kJ/kg per transducer). Creaming behavior was assessed by measuring the thickness of the separated cream layer. Other methods supporting this assessment included the measurement of fat content, backscattering, particle size distribution, and microscopy of samples taken at the bottom and top of the reactor. Most efficient creaming was found after treatment at 0.4 MHz in single and double vertical transducer configurations. Among these configurations, a higher separation rate was obtained when sonicating at 0.4 MHz in a vertical perpendicular double transducer setup. The horizontal transducer configuration promoted creaming at 2 MHz only. Fat globule size increase was observed when creaming occurred. This research highlights the potential for enhanced separation of milkfat in larger scale systems from selected transducer configurations in contact with a dairy emulsion, or emulsion splitting in general.     

Proton diffusion in the superprotonic phase of [(NH4)1 − xRbx]3H(SO4)2 as studied by 1H spin-lattice relaxation

Proton diffusion in [(NH₄)_1 ? xRb_x]₃H(SO₄)₂ (0 < x < 1) has been studied by means of ¹H spin-lattice relaxation times, T₁. The relaxation times were measured at 200.13 MHz in the range of 296–490 K and at 19.65 MHz in the range of 300–470 K. In the high-temperature phase (phase I), translational diffusion of the acidic protons relaxes both the acidic protons and the ammonium protons. Spin diffusion averages the relaxation rate of the two kinds of protons, whereas proton exchange between them are slow. The spin-lattice relaxation times in phase I were analyzed theoretically, and parameters of proton diffusion were obtained. The mean residence time of the acidic protons increases with increase in x for [(NH₄)_1 ? xRb_x]₃H(SO₄)₂ (0 ≤ x ≤ 0.54). Rb₃H(SO₄)₂ does not obey this trend. The results of NMR well explain the macroscopic proton conductivity.     

Heat transfer enhancement using 2 MHz ultrasound

The present work focuses on possible heat transfer enhancement from a heating plate towards tap water in forced convection by means of 2 MHz ultrasound. The thermal approach allows to observe the increase of local convective heat transfer coefficients in the presence of ultrasound and to deduce a correlation between ultrasound power and Nusselt number. Heat transfer coefficient under ultrasound remains constant while heat transfer coefficient under silent conditions increases with Reynolds number from 900 up to 5000. Therefore, heat transfer enhancement factor ranges from 25% up to 90% for the same energy conditions (supplied ultrasonic power = 110 W and supplied thermal power = 450 W). In the same time cavitational activity due to 2 MHz ultrasound emission was characterized from mechanical and chemical viewpoints without significant results. At least, Particle Image Velocimetry (PIV) measurements have been performed in order to investigate hydrodynamic modifications due to the presence of 2 MHz ultrasound. It was therefore possible to propose a better understanding of heat transfer enhancement mechanism with high frequency ultrasound.     

7Li NMR analysis on perovskite structured Li0.15La0.28TaO3

The nanocrystalline perovskite material Li_0.15La_0.28TaO₃ has been synthesized by alkoxide-free Pechini type sol gel method. ⁷Li NMR measurements were carried out using a Bruker Avance 300 spectrometer at 116 MHz over the temperature range 150 to 400 K. Longitudinal spin-lattice relaxation times (T₁) measured by saturation recovery and longitudinal relaxation times in the rotating frame (T_1ρ) measured using the pulse sequence (π/2–spin lock τ acquisition) with lock radio-frequency field υ = 62.5 kHz and the T₂ relaxation time measured by Hahn echo are presented. The static Hahn-echo spectra show two different lithium sites in this perovskite oxide. Further, the relaxation measurements T₁ and T_1ρ show two different types of lithium cations with fast and slow dynamics.     

Proton diffusion in the room-temperature phase of [(NH4)1−xRbx]3H(SO4)2 as studied by 1H spin-lattice relaxation in the rotating frame

Proton diffusion in the room-temperature phase (phase II) of [(NH₄)_1?xRb_x]₃H(SO₄)₂ (0≤x≤1) has been studied by means of ¹H spin-lattice relaxation times in the rotating frame, T_1ρ. The ¹H T_1ρ values were measured at 200.13 MHz in the range of 380–490 K. The ammonium protons and the acidic protons have independent T_1ρ values in the higher temperature range of phase II, suggesting that the spin diffusion between the two species is ineffective. The translational diffusion of the acidic protons is the most dominant mechanism to relax both the ammonium protons and the acidic protons in phase II. The ¹H T_1ρ values in phase II are analyzed theoretically and the motional parameters are obtained. The results of NMR well explain the macroscopic proton conductivity.     

IQ quadrature demodulation algorithm used in heterodyne detection

In order to obtain better detection results of heterodyne, we used phase IQ quadrature demodulation algorithm to process the data which detected by laser heterodyne. Based on laser heterodyne interferometer, processing the data in the interferometer phase IQ quadrature demodulation algorithm from the signal to noise ratio, sampling rate, sampling rate, filter order and cutoff frequency, verify the effects of these system parameters to the phase precision, and choose the best parameters to obtain a better phase precision through experiment as: the signal to noise ratio is 25 dB, the IF signal frequency is 98.3 MHz, 98.5 MHz, 99.1 MHz, 99.5 MHz and 100 MHz, the sampling rate is 512–2048, the cutoff frequency and order of the filter are 0.11 and 40, respectively.     

Impedance spectroscopic studies of an organic semiconductor device incorporating a thin film of highly doped ZnPc with MoO3

We use experimental results of low signal impedance spectroscopy to investigate the conduction mechanism in organic semiconductor, zinc phthalocyanine (ZnPc). The first 10 nm, of a total of 150 nm thermally deposited ZnPc, was doped with molybdenum oxide (MoO₃) by co-evaporation to obtain a 20% doping concentration. The ac electrical parameters were measured at room temperature in the dc bias and frequency ranges of 0–5 V and 100 Hz–0.1 MHz, respectively. The variation of bulk resistance with applied bias presents a clear indication of space charge limited conduction in the fabricated device. The experimental results show a strong frequency dependence of capacitance and loss tangent at low frequencies and high applied bias, while at higher frequencies and low applied bias a weak dependence is observed. Moreover, the ac conductivity shows a strong dependence on frequency and is found to vary as ω^s with the index s≤1.15 suggesting a dominant hopping mechanism of conduction.     

Effects of Zr impurity on microscopic behavior of Hf metal

Hf metal with ∼ 3 wt% Zr impurity has been reinvestigated by perturbed angular correlation (PAC) spectroscopy using a LaBr₃(Ce)–BaF₂ detector set up to understand the microscopic behavior of this metal with temperature. From present measurements, five quadrupole interaction frequencies have been found at room temperature where both pure hcp fraction (∼33%) with 12 nearest neighbor Hf surrounding the probe ¹⁸¹Hf atom and the probe–impurity fraction (∼33%) corresponding to 11 nearest neighbor Hf plus one dissimilar Zr atom are clearly distinguished. At room temperature, the results for quadrupole frequency and asymmetry parameter are found to be ω_Q=51.6(4) Mrad/s, η=0.20(4) for the impurity fraction and ω_Q=46.8(2) Mrad/s, η=0 for the pure fraction with values of frequency distribution width δ=0 for both components. At 77 K, only 1 NN Zr impurity (∼93%) and pure hcp (∼7%) components have been found with a value of δ ∼ 10% for the impurity fraction. A drastic change in microstructural configuration of Hf metal is observed at 473 K where the impurity fraction increases to ∼ 50% and the pure hcp fraction reduces to ∼ 15% with abrupt changes in quadrupole frequencies for both components. The pure fraction then increases with temperature and enhances to ∼50% at 973 K. In the temperature range 473–973 K, quadrupole frequencies for both components are found to decrease slowly with temperature. Using the Arrhenius relation, binding energy (B) for the probe–impurity pair and the entropy of formation are measured from temperature dependent fractions of probe–impurity and pure hcp in the temperature range 473–773 K. The three other minor components found at different temperatures are attributed to crystalline defects.     

Photonic-based instantaneous microwave frequency measurement with extended range

A novel approach to extend the frequency range and improve the resolution of photonic techniques for microwave frequency measurements based on frequency-to-power mapping is demonstrated. The simultaneous use of several amplitude comparison functions allows the extension of the measurement beyond a single monotonic region. Experimental results between 7 and 19 GHz with a resolution better than 100 MHz are presented.     

Noncontact characterization of glucose by a waveguide microwave probe

We investigate the electromagnetic field interaction with a glucose aqueous solution using a microwave dielectric waveguide probe to evaluate the glucose concentrations. A microwave dielectric waveguide probe allows observation of the small variation of the glucose concentration changes in the range of 0–300 mg/ml by measuring the change of the microwave reflection coefficient. We could observe the effect of concentration change of glucose with a detectable resolution up to 0.5 mg/ml at an operating frequency of about f = 2.0–2.5 GHz. The change of the glucose concentration is directly related to the change of the reflection coefficient due to the electromagnetic interaction between the dielectric waveguide resonator and the glucose aqueous solution. The operational principal is explained by a plane-wave solution model. A glucose biosensor using a microwave dielectric waveguide probe provides a unique approach for glucose monitoring.     

Pretreatment of defatted wheat germ proteins (by-products of flour mill industry) using ultrasonic horn and bath reactors: Effect on structure and preparation of ACE-inhibitory peptides

The ultrasonic horn and bath reactors were compared based on production of angiotensin-converting-enzyme (ACE) inhibitory peptides from defatted wheat germ proteins (DWGP). The DWGP was sonicated before hydrolysis by Alcalase. Degree of hydrolysis, ACE-inhibitory activity, surface hydrophobicity, fluorescence intensity, free sulfhydryl (SH), and disulfide bond (SS) were determined. The highest ACE-inhibitory activity of DWGP hydrolysate was obtained at power intensity of 191.1 W/cm² for 10 min in the ultrasonic horn reactor. The fixed frequency of 33 kHz and the sweep frequency of 40 ± 2 kHz resulted in the maximum ACE-inhibitory activity. The combined irradiation of dual fixed frequency (24/68 kHz) produced significant increase in ACE-inhibitory activity compared with single frequency (33 kHz). The ultrasonic probe resulted in significant higher ACE-inhibitory activity compared with ultrasonic bath operating at single or dual fixed and sweep frequencies. The changes in conformation of the DWGP due to sonication were confirmed by the changes in fluorescence intensity, surface hydrophobicity, SH_f and SS contents and they were found in conformity with the ACE-inhibitory activity in case of the ultrasonic horn reactor but not in bath reactor.     

Design of a super wide-band EM wave absorber for a general purpose anechoic chamber

In order to construct an anechoic chamber satisfying international standards for EMI testing, it has been recognized that the absorption characteristics of the EM wave absorber must be higher than 20 dB over the frequency band from 30 MHz to 18 GHz. In this paper, an EM wave absorber with super wide-band frequency characteristics is proposed and designed in order to satisfy the above requirements by using the EMCM and FDTD. As a result, the proposed absorber has absorption characteristics higher than 20 dB over the frequency band from 30 MHz to more than 20 GHz.     

Multispectral 3D phase-encoded turbo spin-echo for imaging near metal: Limitations and possibilities demonstrated by simulations and phantom experiments

To see improvements in the imaging performance near biomaterial implants we assessed a multispectral fully phase-encoded turbo spin-echo (ms3D-PE-TSE) sequence for artifact reduction capabilities and scan time efficiency in simulation and phantom experiments.For this purpose, ms3D-PE-TSE and ms3D-TSE sequences were implemented to obtain multispectral images (± 20 kHz) of a cobalt-chromium (CoCr) knee implant embedded in agarose. In addition, a knee implant computer model and the acquired ms3D-PE-TSE images were used to investigate the possibilities for scan time acceleration using field-of-view (FOV) reduction for off-resonance frequency bins and compressed sensing reconstructions of undersampled data. Both acceleration methods were combined to acquire a + 10 kHz frequency bin in a second experiment.The obtained ms3D-PE-TSE images showed no susceptibility related artifacts, while ms3D-TSE images suffered from hyper-intensity artifacts. The limitations of ms3D-TSE were apparent in the far off-resonance regions (±[10–20] kHz) located close to the implant. The scan time calculations showed that ms3D-PE-TSE can be applied in a clinically relevant timeframe (~ 12 min), when omitting the three central frequency bins. The feasibility of CS acceleration for ms3D-PE-TSE was demonstrated using retrospective reconstructions before combining CS and rFOV imaging to decrease the scan time for the + 10 kHz frequency bin from ~ 10.9 min to ~ 3.5 min, while also increasing the spatial resolution fourfold. The temporally resolved signal of ms3D-PE-TSE proved to be useful to decrease the intensity ripples after sum-of-squares reconstructions and increase the signal-to-noise ratio.The presented results suggest that the scan time limitations of ms3D-PE-TSE can be sufficiently addressed when focusing on signal acquisitions in the direct vicinity of metal implants. Because these regions cannot be measured with existing multispectral methods, the presented ms3D-PE-TSE method may enable the detection of inflammation or (pseudo-)tumors in locations close to the implant.     

Phase errors in FSE signals due to low frequency electromagnetic interference

ObjectiveTo quantitatively evaluate induced phase errors in fast spin echo (FSE) signals due to low frequency electromagnetic inference (EMI).MethodsSpecific form of Bloch equation is numerically solved in time domain for two different FSE pulse sequences (ETL = 8) with two different bandwidths. A single spin is modeled at x = 10 cm, EMI frequencies are simulated from 1 to 1000 Hz and phase errors at different echo times are calculated.ResultsPhase errors in the received echo signals induced by EMI are significantly higher at low frequencies (< 200 Hz) than at high frequencies and the phase errors at low frequencies can be effectively reduced by using high receiving bandwidth.ConclusionPulse sequence bandwidth can be used to control the phase errors in the FSE signals due to low frequency EMI.     

Ultrasonically enhanced fractionation of milk fat in a litre-scale prototype vessel

The ultrasonic fractionation of milk fat in whole milk to fractions with distinct particle size distributions was demonstrated using a stage-based ultrasound-enhanced gravity separation protocol. Firstly, a single stage ultrasound gravity separation was characterised after various sonication durations (5–20 min) with a mass balance, where defined volume partitions were removed across the height of the separation vessel to determine the fat content and size distribution of fat droplets. Subsequent trials using ultrasound-enhanced gravity separation were carried out in three consecutive stages. Each stage consisted of 5 min sonication, with single and dual transducer configurations at 1 MHz and 2 MHz, followed by aliquot collection for particle size characterisation of the formed layers located at the bottom and top of the vessel. After each sonication stage, gentle removal of the separated fat layer located at the top was performed.Results indicated that ultrasound promoted the formation of a gradient of vertically increasing fat concentration and particle size across the height of the separation vessel, which became more pronounced with extended sonication time. Ultrasound-enhanced fractionation provided fat enriched fractions located at the top of the vessel of up to 13 ± 1% (w/v) with larger globules present in the particle size distributions. In contrast, semi-skim milk fractions located at the bottom of the vessel as low as 1.2 ± 0.01% (w/v) could be produced, containing proportionally smaller sized fat globules. Particle size differentiation was enhanced at higher ultrasound energy input (up to 347 W/L). In particular, dual transducer after three-stage operation at maximum energy input provided highest mean particle size differentiation with up to 0.9 μm reduction in the semi-skim fractions. Higher frequency ultrasound at 2 MHz was more effective in manipulating smaller sized fat globules retained in the later stages of skimming than 1 MHz. While 2 MHz ultrasound removed 59 ± 2% of the fat contained in the initial sample, only 47 ± 2% was removed with 1 MHz after 3 ultrasound-assisted fractionation stages.