Resonant Spectroscopy Technique Research Articles

Elastic constants of equiatomic Fe–Ni Invar alloy single crystal

In a disordered fcc structure, the equiatomic Fe–Ni alloy is of great interest as a soft magnetic Invar alloy with a near zero or low thermal expansion coefficient. In the L10 ordered phase, it is of interest as a potential high-performance permanent magnet alloy. In this work, the first detailed measurements of the elastic constants in a [001]-oriented Fe-50 at. % Ni alloy single crystal under a no magnetic field condition were made using the resonant ultrasound spectroscopy technique. The elastic constants measured allow one to understand the nature of atomic bonding in a material and the mechanical response to applied stress. The single crystal sample having a rectangular parallelepiped shape was prepared from a single crystal grown using the vertical Bridgman technique. The elastic constants C11, C12, and C44 were obtained from the resonant frequencies observed over a frequency range of 100–900 kHz. Using these C11, C12, and C44 values, Young’s modulus, shear modulus, bulk modulus, and Poisson’s ratio were calculated to be 99.1 GPa, 73.4 GPa, 176.7 GPa, and 0.20, respectively. The large anisotropy factor of 3.29 highlights the strong directional dependence of the material’s mechanical behavior.

Parts-per-billion-level detection of hydrogen sulfide based on doubly resonant photoacoustic spectroscopy with line-locking

We report on the development of a highly sensitive hydrogen sulfide (H2S) gas sensor exploiting the doubly resonant photoacoustic spectroscopy technique and using a near-infrared laser emitting at 1578.128 nm. By targeting the R(4) transition of H2S, we achieved a minimum detection limit of 10 part per billion in concentration and a normalized noise equivalent absorption coefficient of 8.9 × 10−12 W cm−1 Hz−1/2. A laser-cavity-molecule locking strategy is proposed to enhance the sensor stability for fast measurement when dealing with external disturbances. A comparison among the state-of-the-art H2S sensors using various spectroscopic techniques confirmed the record sensitivity achieved in this work.

Contact-less, non-resonant and high-frequency ultrasonic technique: Towards a universal tool for plant leaf study

Plant-based measurements are recognized as key methods to obtain insightful data in the field. In general, they are labor-intensive and expensive. In this context, Non-Contact Resonant Ultrasonic Spectroscopy technique (NC-RUS) emerged as a powerful alternative that enabled plant water status determination in a non-destructive, non-invasive and rapid way. However, NC-RUS is not applicable to all plant species as it depends on the possibility to excite and sense thickness resonances in the leaves. In this work, we propose and test an ultrasonic technique that can be used in all leaves, regardless of the appearance of thickness resonances. This technique is based on the contactless measurement of through transmitted airborne ultrasonic pulses in the leaves at high-frequencies and in the absence of thickness resonances, to obtain the leaf ultrasonic velocity (vair). It benefits from the facts that: i) at sufficiently high frequencies (typically around 1 MHz) all leaves are non-resonant (so the technique can be applied to both resonant and non-resonant leaves), ii) the use of high-frequencies allows a greater time resolution and a further miniaturization, making possible to apply the technique to small and irregular leaves. Three different signal processing techniques were used to determine the time it takes to the ultrasonic pulse to cross the leaves (time-of-flight) from the measured signals. Two of them operate in time domain: cross-correlation, and edge detection, while the third one makes use of the Fast Fourier Transform (FFT) and operates in the frequency domain: phase-slope. If leaf thickness is also measured, ultrasound velocity can then be worked out. As ultrasound velocity is determined by density and elastic modulus, it is then closely related to water content and turgor pressure. Obtained ultrasound velocities were first validated by comparing them with those obtained by well-established and standard ultrasonic methods: water immersion transmission (vwater) and NC-RUS (vres). The conclusions of this comparison permitted us to propose a novel methodology that combines the three signal processing techniques used to improve robustness and accuracy for the measurement of ultrasound velocity in plant leaves. It is of interest to note that a bias towards higher values of vair compared to vres was observed. This behavior is considered the consequence of the different influence of the leaf layered structure in these two measurements, so this feature can be further used for leaf structure analysis.

Determining the full elastic tensor using resonant ultrasound spectroscopy in extreme environments

Elastic moduli are fundamental thermodynamic susceptibilities that connect directly to thermodynamics, electronic structure and mechanic properties. Thus, determining the changes of elastic moduli as a function of time and temperature is a powerful tool to study a variety of phenomena. The Resonant Ultrasound Spectroscopy (RUS) technique is based on the measurement of mechanical resonance frequencies that can be made with extreme precision and used to compute the elastic moduli without corrections. In this talk, I will give show several examples of the use of RUS in different systems, ranging from magnetic phase transition, determining very small degrees of elastic anisotropy in metals as well as changes in time product of radioactive decay. I will discuss the latest advances made at Los Alamos on measuring and determination of elastic constants. This allow to track the resonance position with high precision, obtaining moduli with an absolute precision of 0.5% and relative changes smaller than part per 10 million.

Elastic properties of additively manufactured alloys

With the advent of metal Additive Manufacturing (AM), or 3D printing, the focus on evaluating and fine-tuning the fabrication process has become crucial. High-resolution volumetric mapping of elastic properties throughout an AM built sample can be done, “biopsy” style, with the highly adaptable Resonant Ultrasound Spectroscopy (RUS) technique. We report results of elastic constants measurements on AM-fabricated Ti64 and CL 80CU bronze (i.e., Cu0.9Sn0.1) alloy with RUS. Despite an easily observable pore distribution, surprisingly sharp spectra and good RUS fits were obtained for both. The average E and G moduli obtained for AM Ti64 at room temperature are ≈104 and ≈39.4 GPa, respectively. The values are only a few percent lower than those of the traditionally manufactured alloy. Moreover, stress-strain measurements on dog-bone samples of Ti64 from the sample batch lead to a value of 101 GPa for E. Heat-treatment of as-manufactured Ti64 samples lead to a slight increase in both moduli. For the investigated bronze, an ≈10% variation of elastic properties within a cross section of a printed sample was observed. The average E and G moduli obtained for AMCL 80CU bronze at room temperature are ≈111 and ≈40.9 GPa, respectively.

Contactless Resonant Cavity Dielectric Spectroscopic Studies of Cellulosic Paper Aging

The current analytical techniques for characterizing printing and graphic arts substrates, particularly those used to date and authenticate provenance, are destructive. This limits the amount of data that can be captured from an individual sample. For samples being evaluated in forensic and archeological investigations, any loss or degradation of the materials is undesirable. Furthermore, it is difficult to produce statistically relevant data for such analytes. We have shown elsewhere that a contactless microwave resonant cavity dielectric spectroscopy technique can discriminate between paper samples made from different plant fiber species based on their lignin content. In this publication, we demonstrate the utility of the contactless resonant cavity dielectric spectroscopy (RCDS) technique in the characterization of naturally and artificially aged paper samples. Based on our experimental results, we suggest that the technique could be used in forensic and archeological investigations of unique paper products.

Elastic moduli reduction in SiC-SiC tubular specimen after high heat flux neutron irradiation measured by resonant ultrasound spectroscopy

The initial results of a post-irradiation examination study conducted on a SiC-SiC tubular specimen irradiated under a high radial heat flux are presented herein. The elastic properties of the specimen were evaluated before and after the irradiation using the resonant ultrasound spectroscopy (RUS) technique. The composite tubular specimen was considered as an orthotropic elastic with nine elastic constants (Young's moduli, shear moduli and Poisson's ratios—three components of each) for representing its full elastic deformation behavior. All the elastic moduli decreased after irradiation; the reduction was as high as 35% in one of the moduli. The significant decrease in the moduli indicates the presence of microcracks. The results from a computational study show significant stress development in the specimen due to irradiation, primarily caused by differential swelling across the thickness of the specimen. The evaluated stresses exceed the proportional limit stress of the material, indicating the likelihood of matrix microcracking, and thus corroborating the results obtained from RUS. X-ray Computed Tomography (XCT) study confirmed the presence of cracks in the irradiated specimen. These cracks occurred at the inner region of the specimen and propagated in axial and hoop directions. These XCT results are in agreement with the RUS results and stress distribution results from the computational study.

Elastic constants identification of irregular hard biological tissue materials using FEM-based resonant ultrasound spectroscopy

This paper aims to apply the resonant ultrasound spectroscopy technique (RUS) combined with micro computed tomography (μ-CT) and finite element method (FEM) to quantify the elastic constants of the irregular hard biological tissue material such as enamel. In this method, the resonant frequencies of an irregular shaped sample tested under stress-free boundary conditions are measured first. Then, micro-computed tomography (μ-CT) is used to acquire three-dimensional (3-D) geometry information of the sample, and the resonant frequencies are calculated with FEM. Thereby, an optimization procedure using the Levenberg-Marquardt algorithm updates the elastic constants in the FEM model until the output natural frequencies from the model fit the results from the RUS experiments. The proposed method has been tested first on a calibration material. To this purpose, titanium has been selected. The elastic constants of a rectangular parallelepiped shaped titanium sample obtained by the conventional RUS method and those of five irregular samples obtained by FEM-based RUS were in good agreement, displaying differences less than 2%. Once the method has been validated on titanium, it was applied to an enamel sample. The results show that the FEM-based RUS method can effectively identify the elastic constants of irregular titanium and enamel samples. This study expands the application range of RUS technology and provides a new method for the measurement of elastic properties of irregular hard biological tissue materials.

Accurate characterization of complete set constants of single domain 0.72Pb(Mg1/3Nb2/3)O3–0.28PbTiO3 single crystal by resonant ultrasound spectroscopy using only one sample

In order to find out the origin of the giant piezoelectric effects of relaxor-PbTiO3 single crystals when poled along nonpolar directions, it is necessary to obtain the complete physical property data of a single domain state. Conventional characterization methods using multiple samples of different geometries often produce inconsistent data set because the domain patterns produced during poling are strongly dependent on the sample geometry. Here, we used the resonant ultrasound spectroscopy (RUS) technique to determine the material constants of a single domain 0.72Pb(Mg1/3Nb2/3)O3–0.28PbTiO3 single crystal, which has a high mechanical quality factor (QM). Errors caused by sample-to-sample variation are avoided because all constants were measured from the same sample. The data set obtained is highly self-consistent, which provides a base for theoretical analysis as well as the input for simulation designs of piezoelectric devices. Comparison with data measured by other methods shows the advantage and higher accuracy of this characterization strategy.

Non-contact ultrasonic resonant spectroscopy resolves the elastic properties of layered plant tissues

This paper describes the application of the wide-band non-contact ultrasonic resonant spectroscopy technique to layered plant tissues (leaves), a method to extract the properties of main component tissues: palisade parenchyma and spongy mesophyll, a verification of the obtained properties, and a discussion of the implications of the observed elastic anisotropy. Transmission coefficient spectra of Ligustrum lucidum leaves with the thickness in the range of 250–850 μm revealing several order thickness resonances have been measured. A leaf acoustic model based on a two-layered structure and a metaheuristic (simulated annealing algorithm) is used to solve the inverse problem. The extracted parameters of these two layers of tissue are consistent with cross-sectional cryo-SEM images and other independent measurements. The extracted resonant frequency and the impedance of each layer explain the origin of the observed resonances. Finally, the elastic modulus of each layer is extracted and analyzed. The presented technique is a unique tool to study (in vivo and in a completely non-invasive way) the ultrasonic, elastic, and viscoelastic properties of layered plant tissues which could lead to a better understanding of the relationship between the tissue microstructure and the tissue function with macroscopic properties and how this may affect water relations.

Electronic structure of Fe, α-Fe2O3 and Fe(NO3)3 × 9 H2O determined using RXES

Resonant X-ray emission spectroscopy (RXES) technique was applied to probe electronic states of three Fe compounds: Fe, α-Fe2O3 (hematite) and Fe(NO3)3×9 H2O (ferric nitrate) around Fe K-absorption edge with simultaneous detection of Kβ and valence-to-core transitions. We show that deep insights on the valence and conduction band position, such as main orbital contribution to band-gap formation and ligand orbital contributions, can be retrieved from RXES data. Moreover applicability of Kβ and valence-to-core RXES measurements to extract band gap energies is demonstrated. Obtained results were supplemented with ab initio calculations allowing precise determination of orbital contributions to the measured spectral features. Good agreement with experimental results has shown that proposed approach is promising tool in further applications.

Characterizing full matrix constants of piezoelectric single crystals with strong anisotropy using two samples

Although the self-consistency of the full matrix material constants of a piezoelectric sample obtained by the resonant ultrasonic spectroscopy technique can be guaranteed because all constants come from the same sample, it is a great challenge to determine the constants of a piezoelectric sample with strong anisotropy because it might not be possible to identify enough resonance modes from the resonance spectrum. To overcome this difficulty, we developed a strategy to use two samples of similar geometries to increase the number of easy identifiable modes. Unlike the IEEE resonance methods, sample-to-sample variation here is negligible because the two samples have almost the same dimensions, cut from the same specimen and poled under the same conditions. Using this method, we have measured the full matrix constants of a [011]c poled 0.71Pb(Mg1/3Nb2/3)O3-0.29PbTiO3 single crystal, which has 17 independent constants. The self-consistency of the obtained results is checked by comparing the calculated elastic stiffness constants c33D, c44D, and c55D with those directly measured ones using the ultrasonic pulse-echo method.

Characterization of Full Set Material Constants and Their Temperature Dependence for Piezoelectric Materials Using Resonant Ultrasound Spectroscopy

During the operation of high power electromechanical devices, a temperature rise is unavoidable due to mechanical and electrical losses, causing the degradation of device performance. In order to evaluate such degradations using computer simulations, full matrix material properties at elevated temperatures are needed as inputs. It is extremely difficult to measure such data for ferroelectric materials due to their strong anisotropic nature and property variation among samples of different geometries. Because the degree of depolarization is boundary condition dependent, data obtained by the IEEE (Institute of Electrical and Electronics Engineers) impedance resonance technique, which requires several samples with drastically different geometries, usually lack self-consistency. The resonant ultrasound spectroscopy (RUS) technique allows the full set material constants to be measured using only one sample, which can eliminate errors caused by sample to sample variation. A detailed RUS procedure is demonstrated here using a lead zirconate titanate (PZT-4) piezoceramic sample. In the example, the complete set of material constants was measured from room temperature to 120 °C. Measured free dielectric constants and were compared with calculated ones based on the measured full set data, and piezoelectric constants d15 and d33 were also calculated using different formulas. Excellent agreement was found in the entire range of temperatures, which confirmed the self-consistency of the data set obtained by the RUS.

Characterization of Full Set Material Constants and Their Temperature Dependence for Piezoelectric Materials Using Resonant Ultrasound Spectroscopy.

During the operation of high power electromechanical devices, a temperature rise is unavoidable due to mechanical and electrical losses, causing the degradation of device performance. In order to evaluate such degradations using computer simulations, full matrix material properties at elevated temperatures are needed as inputs. It is extremely difficult to measure such data for ferroelectric materials due to their strong anisotropic nature and property variation among samples of different geometries. Because the degree of depolarization is boundary condition dependent, data obtained by the IEEE (Institute of Electrical and Electronics Engineers) impedance resonance technique, which requires several samples with drastically different geometries, usually lack self-consistency. The resonant ultrasound spectroscopy (RUS) technique allows the full set material constants to be measured using only one sample, which can eliminate errors caused by sample to sample variation. A detailed RUS procedure is demonstrated here using a lead zirconate titanate (PZT-4) piezoceramic sample. In the example, the complete set of material constants was measured from room temperature to 120 °C. Measured free dielectric constants and were compared with calculated ones based on the measured full set data, and piezoelectric constants d15 and d33 were also calculated using different formulas. Excellent agreement was found in the entire range of temperatures, which confirmed the self-consistency of the data set obtained by the RUS.

High temperature resonant ultrasound spectroscopy study on Lead Magnesium Niobate—Lead Titanate (PMN-PT) relaxor ferro-electric material

Lead magnesium niobate-lead titanate [(1-x)PbMg1/3Nb2/3O3-xPbTiO3] is a perovskite relaxor ferroelectric material exhibiting superior electromechanical coupling compared to the conventional piezoelectric materials. In this work, non-poled single crystal PMN-PT material with the composition near morphotropic phase boundary (MPB) was investigated in the temperature range of 400 K—800 K where the material is reported to be in the cubic phase. High temperature resonant ultrasound spectroscopy (HT-RUS) technique was used to probe temperature dependency of elastic constants derived from the measured resonant modes. Non-monotonic resonant frequency trends in the temperature regime indicate stiffening of the material, followed by gradual softening typically observed in heated materials. Elastic constants confirmed this stiffening in the temperature range of 400 K—673 K, where the stiffness constants C11 and C44 increased approximately by 40% and 33% respectively. Acoustic attenuation, derived from the quality factor (Q), exhibits a minimum around the temperature where the stiffness is maximum and, significantly higher attenuation observed at temperatures below 400 K. The temperature range 395 K—405 K was identified as a transition temperature range, where the material showed an abrupt change in the resonant spectrum and, the material emerges from the MPB characterized by this very high acoustic attenuation. This transition temperature compares favorably with dielectric constant measurements reported in the literature.

In-situ Young's moduli of the constitutive layers in a solid oxide fuel cell

In-situ Young's moduli of thin constituent layers of a solid oxide fuel cell (SOFC) are needed to estimate the mechanical reliability of the fuel cell unit. Because a robust technique to measure the same is not available, an improved methodology is proposed to determine the in-situ Young's moduli of thin ceramic layers of a substrate-supported SOFC. The measured Young's moduli of the constituent layers were found to be close to those of corresponding bulk materials using the resonant ultrasound spectroscopy (RUS) technique but were different from the values obtained using nanoindentation.

Instrumentação para espectroscopia de ressonância de ultrassom

A técnica de espectroscopia de ressonância de ultrassom possibilita a determinação simultânea de todos os componentes do tensor de elasticidade do material que constitui a amostra. Neste trabalho é descrita a montagem de um dispositivo de espectroscopia de ressonância de ultrassom automatizado, que possibilita a análise de pequenas amostras na forma de paralelepípedos, cilindros ou esferas. A aplicação deste dispositivo é exemplificada com a determinação das constantes elásticas de amostras policristalinas de alumina e níquel. Os resultados obtidos diferem dos valores esperados em, no máximo, 2,6% e 0,91% para a alumina e níquel, respectivamente, e ilustram a aplicação deste dispositivo na determinação das constantes elásticas de pequenas amostras.

Non Destructive Characterization of Cortical Bone Micro-Damage by Nonlinear Resonant Ultrasound Spectroscopy

The objective of the study was to evaluate the ability of a nonlinear ultrasound technique, the so-called nonlinear resonant ultrasound spectroscopy (NRUS) technique, for detecting early microdamage accumulation in cortical bone induced by four-point bending fatigue. Small parallelepiped beam-shaped human cortical bone specimens were subjected to cyclic four-point bending fatigue in several steps. The specimens were prepared to control damage localization during four-point bending fatigue cycling and to unambiguously identify resonant modes for NRUS measurements. NRUS measurements were achieved to follow the evolution of the nonlinear hysteretic elastic behavior during fatigue-induced damage. After each fatigue step, a small number of specimens was removed from the protocol and set apart to quantitatively assess the microcrack number density and length using synchrotron radiation micro-computed tomography (SR-µCT). The results showed a significant effect of damage steps on the nonlinear hysteretic elastic behavior. No significant change in the overall length of microcracks was observed in damaged regions compared to the load-free control regions. Only an increased number of shortest microcracks, those in the lowest quartile, was noticed. This was suggestive of newly formed microcracks during the early phases of damage accumulation. The variation of nonlinear hysteretic elastic behavior was significantly correlated to the variation of the density of short microcracks. Our results suggest that the nonlinear hysteretic elastic behavior is sensitive to early bone microdamage. Therefore NRUS technique can be used to monitor fatigue microdamage progression in in vitro experiments.

Properties of Fr-like Th3+from rf spectroscopy of high-LTh2+Rydberg ions

Relative positions of twenty $n=28$ Rydberg levels of Th${}^{2+}$ with $L=9$, 10, 11, and 12 were determined with sub-MHz precision using the rf-RESIS (resonant excitation Stark ionization spectroscopy) technique. The pattern of binding energies was analyzed with the effective potential model, modified to account for significant nonadiabatic effects. The analysis yielded measurements of several properties of the Fr-like Th${}^{3+}$ core ion, including the quadrupole moment, $Q=0.5931$(14) a.u.; hexadecapole moment, \ensuremath{\Pi} $=$ \ensuremath{-}0.69(28) a.u.; $g$ factor, ${g}_{J}=1.24$(48); scalar and tensor dipole polarizabilities, \ensuremath{\alpha}${}_{D}$${}_{,0}=15.224$(33) a.u. and \ensuremath{\alpha}${}_{D}$${}_{,2}$ $=$ \ensuremath{-}5.30(11) a.u.; scalar quadrupole polarizability, \ensuremath{\alpha}${}_{Q}$${}_{,0}=60$(15) a.u.; and the reduced dipole and octupole matrix elements connecting the ground 5$f$ ${}^{2}$${F}_{5/2}$ level with the low-lying 6$d$ ${}^{2}$${D}_{3/2}$ level, $|{\ensuremath{\langle}}^{2}{F}_{5/2}||{\mathrm{M}}^{[1]}|{|}^{2}{D}_{3/2}\ensuremath{\rangle}|=1.436(2)$ a.u. and $|{\ensuremath{\langle}}^{2}{F}_{5/2}||{\mathrm{M}}^{[3]}|{|}^{2}{D}_{3/2}\ensuremath{\rangle}|=3.3(1.1)$ a.u. The measured properties are compared with theoretical predictions.

비선형 초음파공명 특성을 이용한 미세균열 탐지

기존 비파괴평가 기술의 결함 탐지 한계를 극복하기 위하여 비선형 초음파공명 특성을 이용한 미세 균열 진단 기술을 개발하였다. 가진 전압에 따른 초음파공명 주파수의 천이현상과 정규화 공명 진폭 감소 현상을 비선형 초음파공명 특성 파라미터로 제안하였으며 이를 실험적으로 확인하였다. CT 시편에 피로시험을 통하여 미세한 자연 균열을 생성하였으며 피로 사이클 단계마다 초음파공명주파수와 정규화 공명진폭의 변화를 측정하였다. 무결함 또는 10 <TEX>${\mu}m$</TEX> 정도의 매우 미세한 균열이 존재하는 시편에서는 초음파공명 주파수 천이현상이나 정규화 공명 진폭의 변화가 나타나지 않는 반면에 30 <TEX>${\mu}m$</TEX>급 이상의 미세 균열 시편에서는 균열 크기가 증가함에 따라 초음파공명주파수의 천이 현상이나 정규화 공명 진폭의 감소량이 증가함을 확인하였다. In order to overcome the detection limit by the current nondestructive evaluation technology, a nonlinear resonant ultrasound spectroscopy(NRUS) technique was applied for detection of micro-scale cracks in a material. A down-shift of the resonance frequency and a variation of normalized amplitude of the resonance pattern were suggested as the nonlinear parameter for detection of micro-scale cracks in a materials. A natural-like crack were produced in a standard compact tension(CT) specimen by a low cycle fatigue test and the resonance patterns were acquired in each fatigue step. As the exciting voltage increases, a down-shift of resonance frequency were increases as well as the normalized amplitude decrease. This nonlinear effects were significant and even greater in the cracked specimen, but not observed in a intact specimen.