Modulated Photothermal Radiometry Research Articles

In-situ thermophysical measurement of flowing molten chloride salt using modulated photothermal radiometry

Molten salts are leading candidates for high-temperature heat transfer fluids (HTFs) for thermal energy storage and conversion systems in concentrated solar power (CSP) and nuclear energy power plants. The ability to probe molten salt thermal transport properties in both stationary and flowing status is important for the evaluation of their heat transfer performance under realistic operational conditions, including the temperature range and potential degradation due to corrosion and contamination. However, accurate thermal transport properties are usually challenging to obtain even for stagnant molten salts due to different sources of errors from convection, radiation, and corrosion, let alone at flowing status. To the best of authors’ knowledge, there is no available in-situ technique for measuring flowing molten salt thermal conductivity. Here, we report the first in-situ flowing molten salt thermal conductivity measurement using modulated photothermal radiometry (MPR). We could successfully perform the first in-situ thermal conductivity measurement of flowing molten NaCl-KCl-MgCl2 in the typical operating temperature (520 and 580 °C) with flow velocities ranging from around 0.3 to 1.0 m s−1. The relative change of the molten salt thermal conductivity was measured. Gnielinski’s correlation was also used to estimate the heat transfer coefficient h of the flowing NaCl-KCl-MgCl2 in the given experimental condition. The work showed the potential of the MPR technique serving as an in-situ diagnostics tool to evaluate the heat transfer performance of flowing molten salts and other high-temperature HTFs.

Thermal imaging by scanning photothermal radiometry.

In this work, a modulated photothermal radiometry principle is applied in a scanning configuration. This technique was developed with the aim of performing imaging and thermal characterization at the microscale and exploring characteristic times lower than those accessible by infrared thermography. The use of a heat source smaller than the measurement area provides high sensitivity to in-plane heat diffusion. Application to quantitative thermal characterization of advanced micro-structured materials is demonstrated.

Thermal conductivity measurement using modulated photothermal radiometry for nitrate and chloride molten salts

Molten salts are being used or explored for thermal energy storage and conversion systems in concentrating solar power and nuclear power plants. Thermal conductivity of molten salts is an important thermophysical property dictating the performance and cost of these systems, but its accurate measurement has been challenging, as evidenced by wide scattering of existing data in literature. The corrosive and conducting nature of these fluids also leads to time consuming sample preparation processes of many contact-based measurements. Here, we report the measurement of thermal conductivity of molten salts using a modulated photothermal radiometry (MPR) technique, which is a laser-based, non-contact, frequency-domain method adopted for molten salts for the first time. By unitizing the advantages of front side sensing of frequency-domain measurements and the vertical holder orientation, the technique can minimize the natural convection and salt creeping effects, thus yielding accurate molten salt thermal conductivity . The MPR technique is first calibrated using standard molten materials including paraffin wax and sulfur. It is then applied on measuring pure nitrate salts (NaNO3 and KNO3), solar salt (NaNO3–KNO3 mixture), and chloride salt (NaCl–KCl–MgCl2). The measurement results are compared with data from literature, especially those obtained from laser flash analysis (LFA). Our results demonstrate that the MPR is a convenient and reliable technique of measuring thermal conductivity of molten salts. Accurate thermal conductivity data of molten salts will be valuable in developing the next-generation high-temperature thermal energy storage and conversion systems.

Recent Progress in Modulated Photothermal Radiometry

In this review, the emerging work using a technique known as modulated photothermal radiometry (MPTR) is evaluated. As MPTR has matured, the previous discussions on theory and modeling have become increasingly limited in their applicability to the current state of the art. After a brief history of the technique, the currently used thermodynamic theory is explained, highlighting the commonly applied simplifications. The validity of the simplifications is explored via modeling. Various experimental designs are compared, and the differences are explored. New applications, as well as emerging analysis techniques, are presented to emphasize the trajectory of MPTR.

Film Thicknesses Influence on the Interfacial Thermal Resistances within Ge‐Rich Ge2Sb2Te5/Ge2Sb2Te5 Multilayers

Phase change memories (PCRAM) are often made of chalcogenide alloys in the form of multilayer systems (MLS). The mostly used alloys are Ge2Sb2Te5 and Ge‐rich Ge2Sb2Te5. The current article reports on the thermal characterization of very thin (<5 nm) Ge‐rich Ge2Sb2Te5/Ge2Sb2Te5 MLS by modulated photothermal radiometry (MPTR). The MPTR method allows for the investigation of such samples by determining, with an inverse method, the total thermal resistance of the stack deposited on the substrate. With the measurement of the total thermal resistance, it is possible to determine the thermal conductivity of the deposit and the interfacial thermal resistances between layers. The interfacial thermal resistance between Ge‐rich Ge2Sb2Te5/Ge2Sb2Te5 is characterized, which is an important parameter to reduce the energy cost of the PCRAM functioning. It is also possible to highlight a decrease in interface quality inside the MLS after the beginning of the phase transition around 250 °C.

Response to “Comment on ‘Sizing the depth and width of ideal delaminations using modulated photothermal radiometry’” [J. Appl. Phys. 132, 106191 (2022)

Response to “Comment on ‘Sizing the depth and width of ideal delaminations using modulated photothermal radiometry’” [J. Appl. Phys. 132, 106191 (2022)

Sizing the depth and width of ideal delaminations using modulated photothermal radiometry

Delaminations, buried defects parallel to the sample surface, reduce the material stiffness and the structure reliability. Photothermal methods, based on exciting the surface by a light beam and analyzing the resulting temperature rise, have been extensively used for detecting delaminations and sizing their depth. However, less attention has been paid to the sizing of the delamination width. In this work, we use modulated photothermal radiometry (PTR) to size the depth and width of narrow delaminations by fitting the theoretical temperature expression to the experimental frequency spectrum of the PTR signal. We have established a detectability limit: for good thermal conductors, submicronic delaminations can be sized down to 10 mm, whereas for thermal insulators, it is difficult to go below 0.5 mm. Experiments on calibrated delaminations confirm these predictions.

In-situ thermal transport measurement of flowing fluid using modulated photothermal radiometry

In situ thermal transport measurement of flowing fluid could be useful for the characterization and diagnosis of practical thermal systems such as fluid heat exchangers and thermal energy storage systems. Despite abundant reports on the ex-situ thermal conductivity measurement of stagnant fluids, a suitable technique for the thermal conductivity measurement of flowing fluid has been rarely reported. This paper presents the thermal conductivity measurement of flowing fluid within a pipe using a non-contact modulated photothermal radiometry (MPR) technique, where the surface of the pipe is heated by an intensity-modulated laser and the heat diffuses into the fluid with suitable modulation frequency. We design a tube section with small wall thickness suitable for the MPR measurements to maximize the sensitivity of the thermal response to the fluid properties while minimizing the lateral heat spreading effect. Intrinsic thermal conductivity of different fluids was obtained within a proper range of frequency and flow velocity where the forced convection effect is negligible. The forced convection effect became prominent at high flowing velocity and at low modulation frequency, leading to higher effective thermal conductivity of the fluid. It is found that the intrinsic thermal conductivity could be obtained when the flow velocity is less than 100 mm/sec and ReD1/2Pr1/3 < 100 for DI water and Xceltherm oil under the specified experimental conditions, where ReD is the Reynolds number and Pr is the Prandtl number.

Measurement of High-temperature Thermophysical Properties of Bulk and Coatings Using Modulated Photothermal Radiometry

This paper presents the development of instrumentation for the measurement of high-temperature thermal conductivity of bulk and coatings using a modulated photothermal radiometry (MPR) method, where a sample is heated by an intensity-modulated laser to probe into different layers of the sample. While MPR has been previously established, most of the prior studies only focus on the measurement at room temperature. The MPR has not been well studied for measurements of bulk and coating materials at high temperatures, which are increasingly important for a multitude of applications, such as materials used in the concentrating solar power (CSP) plants and the nuclear reactors. MPR is a non-contact technique that utilizes the intrinsic thermal emission from the specimens for thermometry, which is favorable for measurements at high temperatures in harsh environment. The authors designed and utilized a sample holder suitable for high temperature measurement up to 973 K with good temperature uniformity within the sample. The high-temperature MPR setup was validated by measuring bulk materials with known thermal conductivity. The setup and technique were then extended to the measurement of black solar-absorbing coatings of 10 to 50 μm thick on various substrates by modulating the frequency of the laser heating beam and the thermal penetration depth. The studies showed that thermal conductivities of typical solar-absorbing coatings are 0.4 ~ 0.8 W m−1 K−1, indicating a possibly large temperature drop within the coating under high solar irradiation flux, such as over 1000-sun for central solar towers in CSP plants.

Heat Capacity and Anisotropic Thermal Conductivity in Cr2AlC Single Crystals at High Temperature

The temperature dependences of both heat capacity and thermal conductivity in nanolamellar Cr2AlC single crystals are measured using modulated photothermal radiometry and compared to first-principl...

Thermal conductivity of amorphous and crystalline GeTe thin film at high temperature: Experimental and theoretical study

Thermal transport properties bear a pivotal role in influencing the performance of phase change memory (PCM) devices, in which the PCM operation involves fast and reversible phase change between amorphous and crystalline phases. In this paper, we present a systematic experimental and theoretical study on the thermal conductivity of GeTe at high temperatures involving fast change from amorphous to crystalline phase upon heating. Modulated photothermal radiometry (MPTR) is used to experimentally determine thermal conductivity of GeTe at high temperatures in both amorphous and crystalline phases. Thermal boundary resistances are accurately taken into account for experimental consideration. To develop a concrete understanding of the underlying physical mechanism, rigorous and in-depth theoretical exercises are carried out. For this, first-principles density functional methods and linearized Boltzmann transport equations (LBTE) are employed using both direct and relaxation time based approach (RTA) and compared with that of the phenomenological Slack model. The amorphous phase experimental data has been described using the minimal thermal conductivity model with sufficient precision. The theoretical estimation involving direct solution and RTA method are found to retrieve well the trend of the experimental thermal conductivity for crystalline GeTe at high temperatures despite being slightly overestimated and underestimated, respectively, compared to the experimental data. A rough estimate of vacancy contribution has been found to modify the direct solution in such a way that it agrees excellently with the experiment. Umklapp scattering has been determined as the significant phonon-phonon scattering process. Umklapp scattering parameter has been identified for GeTe for the whole temperature range which can uniquely determine and compare Umklapp scattering processes for different materials

Investigation of Thermal Properties of High-Density Polyethylene/Aluminum Nanocomposites by Photothermal Infrared Radiometry

In this study, thermal properties of high-density polyethylene (HDPE) filled with nanosized Al particles (80 nm) were investigated. Samples were prepared using melt mixing method up to filler volume fraction of 29 %, followed by compression molding. By using modulated photothermal radiometry (PTR) technique, thermal diffusivity and thermal effusivity were obtained. The effective thermal conductivity of nanocomposites was calculated directly from PTR measurements and from the measurements of density, specific heat capacity (by differential scanning calorimetry) and thermal diffusivity (obtained from PTR signal amplitude and phase). It is concluded that the thermal conductivity of HDPE composites increases with increasing Al fraction and the highest effective thermal conductivity enhancement of 205 % is achieved at a filler volume fraction of 29 %. The obtained results were compared with the theoretical models and experimental data given in the literature. The results demonstrate that Agari and Uno, and Cheng and Vachon models can predict well the thermal conductivity of HDPE/Al nanocomposites in the whole range of Al fractions.

Thermal conductivity of carbon doped GeTe thin films in amorphous and crystalline state measured by modulated photo thermal radiometry

The thermal conductivity and thermal boundary resistance of GeTe and carbon doped GeTe thin films, designed for phase change memory (PCM) applications, were investigated by modulated photo thermal radiometry. It was found that C doping has no significant effect on the thermal conductivity of these chalcogenides in amorphous state. The thermal boundary resistance between the amorphous films and SiO2 substrate is also not affected by C doping. The films were then crystallized by an annealing at 450°C as confirmed by optical reflectivity analysis. The thermal conductivity of non-doped GeTe significantly increases after crystallization annealing. But, surprisingly the thermal conductivity of the crystallized C doped GeTe was found to be similar from that of the amorphous state and independent of C concentration. As for the amorphous phase, C doping does not affect the thermal boundary resistance between the crystalline GeTe films and SiO2 substrate. This behaviour is discussed thanks to XRD and FTIR analysis. In particular, XRD shows a decrease of crystalline grain size in crystalline films as C concentration is increased. FTIR analysis of the film before and after crystallization evidenced that this evolution could be attributed to the disappearing of Ge-C bonds and migration of C atoms out of the GeTe phase upon crystallization, limiting then the growth of GeTe crystallites in C-doped films.

Evolution of thermal conductivity of In3Sbβ Teγ thin films up to 550 °C

The temperature dependent thermal conductivity of In–Sb–Te thin films has been measured by modulated photothermal radiometry in the 20–550 °C range for samples with different Te content. Significant changes with temperature are observed and ascribed to a sequence of structural transformations on the basis of in‐situ Raman spectra. The data suggest that the as‐deposited material consisting of a mixture of polycrystalline InSb0.8Te0.2and amorphous Te first undergoes a progressive crystallization of the amorphous part, mostly above 300 °C. Further increase in temperature above 460 °C leads, for higher Te content in the alloy, to the formation of crystalline In3SbTe2, intertwined with a less conductive compound, possibly InTe and/or InSb. Upon cooling to room temperature, the initial polycrystalline InSb0.8Te0.2phase is mostly recovered along with other compounds, with a slightly higher thermal conductivity than that of the as deposited material. (© 2016 WILEY‐VCH Verlag GmbH &amp;Co. KGaA, Weinheim)

Thermal conductivity measurements of thin films at high temperature modulated photothermal radiometry at LNE

A new metrological facility devoted to the thermal conductivity measurements up to 1000 °C for thin films (from few tens nanometers to few micrometers thick) deposited on substrate has been recently designed at LNE. Its measurement principle is based on the infrared modulated photothermal radiometry technique (MPTR). This device has been applied to the thermal characterization of industrially relevant chalcogenide thin films (Ge2Sb2Ti5) up to 400 °C. This work, performed in the frame of the European joint research project “Thin Films,” seeks to improve the traceability to the International System of Units (SI) as well as the reliability of this type of measurements at sub-micrometer scale.

Thermal Characterization of Diamond Films through Modulated Photothermal Radiometry

Diamond (Dia) films are promising heat-dissipative materials for electronic packages because they combine high thermal conductivity with high electrical resistivity. However, precise knowledge of the thermal properties of the diamond films is crucial to their potential application as passive thermal management substrates in electronics. In this study, modulated photothermal radiometry in a front-face configuration was employed to thermally characterize polycrystalline diamond films deposited onto silicon (Si) substrates through laser-assisted combustion synthesis. The intrinsic thermal conductivity of diamond films and the thermal boundary resistance at the interface between the diamond film and the Si substrate were investigated. The results enlighten the correlation between the deposition process, film purity, film transverse thermal conductivity, and interface thermal resistance.

Using pulsed and modulated photothermal radiometry to measure the thermal conductivity of thin films

Two techniques of photothermal radiometry (PTR) in front face configuration were used to determine the thermal conductivity of thin nanocrystalline films. The first technique relies on using modulated laser beam as a heating source. The second is based on pulsed laser heating where the pulse can be assimilated to a Dirac function. In the two measurement setups, the infrared radiation emitted from the heated surface of the sample is measured by an infrared detector. The thermal conductivity of CrN thin films prepared with various thicknesses by magnetron sputtering on silicon substrates was investigated by both techniques showing a dependence on the film microstructure. The thermal resistance at the film-substrate interface and intrinsic thermal conductivity of the films were identified by the two techniques and are in a very good agreement. In addition to the interface thermal resistance, the measurements revealed lower thermal conductivity of very thin films that can be attributed to presence of high amount of grain boundaries and other structural defects.

Simultaneous Measurement of Thermal Diffusivity and Optical Absorption Coefficient of Solids Using PTR and PPE: A Comparison

Modulated photothermal radiometry (PTR) and a modulated photopyroelectric (PPE) technique have been widely used to measure the thermal diffusivity of bulk materials. The method is based on illuminating the sample with a plane light beam and measuring the infrared emission with an infrared detector (PTR) or the electric voltage produced by a pyroelectric sensor in contact with the sample (PPE). The amplitude and phase of both photothermal signals are recorded as a function of the modulation frequency and then fitted to the theoretical model. In this work, we compare the ability of modulated PTR and PPE to retrieve simultaneously the thermal diffusivity and the optical absorption coefficient of homogeneous slabs. In order to eliminate the instrumental factor, self-normalization is used, i.e., the ratio of the photothermal signal recorded at the rear and front surfaces. The influence of the multiple reflections of the light beam and the transparency to infrared wavelengths are analyzed. Measurements performed on a wide variety of homogeneous materials, transparent and opaque, good and bad thermal conductors, confirm the validity of the method. The advantages and disadvantages of both techniques are discussed.

Preparation and photothermal characterization of nanocomposites based on high density polyethylene filled with expanded and unexpanded graphite: Particle size and shape effects

This work aimed at thermal transport characterization of high density polyethylene (HDPE) filled with 5 and 50 μm expanded graphite (EG) particles and with 0.4 μm unexpanded graphite (UG) particles. Sample platelets were produced by melt mixing followed by compression molding. Thermal conductivity k was determined by combining measurements of density, specific heat capacity and thermal diffusivity, the latter by modulated photothermal radiometry (PTR). Starting from an effective medium approximation model, we derived a linearized expression for the effective k of composites with low particle charge. It explains the unusually high experimental k values (up to four-fold increase) as the effect of strongly non-spherical EG particles (aspect ratio 1/p = 110–290). Larger particle sizes produce higher k enhancement, while the interfacial thermal resistance (Rbd = 2.1⋅10−7 m2⋅K/W) has an opposite effect. The same model is consistent with experimental k for low particle charge HDPE/UG composites. At higher particle charge the model fails due to particle interaction leading to validity break of the effective medium approximation.

Simultaneous measurement of thermal diffusivity and optical absorption coefficient using photothermal radiometry. I. Homogeneous solids

Modulated photothermal radiometry (PTR) has been widely used to measure the thermal diffusivity of bulk materials. The method is based on illuminating the sample with a plane light beam and measuring the infrared emission with an infrared detector. The amplitude and phase of the PTR voltage is recorded as a function of the modulation frequency and then fitted to the theoretical model. In this work, we test the ability of modulated PTR to retrieve simultaneously the thermal diffusivity and the optical absorption coefficient of homogeneous slabs. In order to eliminate the instrumental factor, self-normalization is used, i.e., the ratio of the PTR signal recorded at the rear and front surfaces. The influence of the multiple reflections of the light beam, the heat losses, and the transparency to infrared wavelengths are analyzed. Measurements performed on a wide variety of homogeneous materials, covering the whole range from transparent to opaque, confirm the validity of the method. In Part II of this work, the method is extended to multilayered materials.