Jianqin Zhou

Arrhenius behavior of hydrocarbon fuel photochemical reaction rates by thermal lens spectroscopy

The temperature dependence of thermo-optical and photochemical reaction properties of hydrocarbon fuels is investigated using thermal lens spectroscopy. We consider the time dependence of the absorption coefficient due to the photoinduced chemical reaction (PCR) and species diffusion to evaluate nonequilibrium characteristics of the samples. The measured temperature dependences of the reaction rates are found to follow the Arrhenius correlation. Experimental results for thermophysical properties of the samples and an analysis of the connection between PCR properties and the chemistry of the samples are also presented.

An open-photoacoustic-cell method for thermal characterization of a two-layer system

In the present work, we use an open-photoacoustic-cell (OPC) operating at high frequency to measure thermal properties of two-layer system samples. Photothermal deflection technique is also employed to measure the samples. The effective thermal diffusivity measured using the OPC method is interpreted using the concept of effective thermal resistance for a series two-layer system. The results show the reliability of the photoacoustic method for a complete thermal characterization of the samples. In addition, by varying the sample effective thickness, the thermal diffusivity and conductivity of each layer are precisely determined. The effective thermal diffusivity, thermal conductivity, and specific heat of a porous catalyst layer (thickness varying from 13 to 53 μm) deposited on an aluminum foil (53 μm in thickness) were thus measured and found to be (3.7±0.3)×10−3 cm2/s, (7.5±0.7)×10−3 W/cm K, and (1.6±0.2) J/gK, respectively.

Thermal-lens study of photochemical reaction kinetics.

We consider the time dependence of the absorption coefficient due to the photoinduced chemical reaction (PCR) and species diffusion to calculate the temperature rise in the thermal-lens (TL) effect. The TL signal at the detector plane is also calculated. This theoretical approach removes the restriction that the PCR time constant is much greater than the characteristic TL time constant, which was assumed in a previously published model. Hydrocarbon fuel and aqueous Cr(VI) samples are investigated, and quantitative experimental results for the thermal, optical, and PCR properties are obtained. While similar results were obtained for the Cr(VI) solution using the previous and present models, the relative difference between the PCR time constants extracted from the same experimental data for a hydrocarbon fuel sample is found to be more than 220%. This demonstrates the significant difference of the two models.

Top-hat cw-laser-induced time-resolved mode-mismatched thermal lens spectroscopy for quantitative analysis of low-absorption materials

Thermal lens spectroscopy is a highly sensitive and versatile photothermal technique for material analysis, providing optical and thermal properties. To use less expensive multimode non-Gaussian lasers for quantitative analysis of low-absorption materials, this Letter presents a theoretical model for time-resolved mode-mismatched thermal lens spectroscopy induced by a cw laser with a top-hat profile. The temperature profile in a sample was calculated, and the intensity of the probe beam center at the detector plane was also derived using the Fresnel diffraction theory. Experimental validation was performed with glass samples, and the results were found well consistent with literature values of the thermo-optical properties of the samples.

The Effect of Relative Humidity on Binary Gas Diffusion

The dependence of diffusion coefficient of O2-N2 mixture in the presence of water vapor was experimentally determined as a function of relative humidity (RH) with different temperatures using an in-house made Loschmidt diffusion cell. The experimental results showed that O2-N2 diffusion coefficient increased more than 17% when RH increased from 0% to 80% at 79 degrees C. In the experiments, the RH in both top and bottom chambers of the diffusion cell were the same, and the pressure inside the diffusion cell was kept as ambient pressure (1 atm.). Maxwell-Stefan theory was employed to analyze the mass transport in the diffusion cell, and found that there was no effective water vapor diffusion taking place, indicating that the gas diffusion in this ternary (O2-N2-water vapor) system could be considered binary gas (O2-N2) diffusion. The Fuller, Schettler, and Giddings (FSG) empirical equation of the kinetic theory of gases was generalized to accommodate the dependence of the binary diffusion coefficient on the RH. The prediction of the generalized equation was found to be consistent with experimental results with the difference of less than 1.5%, showing that the generalized equation could be applied to calculate the diffusion coefficients of the binary gaseous mixture with different temperature and RH values. The effect of water vapor on the increase of O2-N2 diffusion coefficient was discussed using molecule theory.

Time-resolved thermal mirror technique with top-hat cw laser excitation

A theoretical model was developed for time-resolved thermal mirror spectroscopy under top-hat cw laser excitation that induced a nanoscale surface displacement of a low absorption sample. An additional phase shift to the electrical field of a TEM(00) probe beam reflected from the surface displacement was derived, and Fresnel diffraction theory was used to calculate the propagation of the probe beam. With the theory, optical and thermal properties of three glasses were measured, and found to be consistent with literature values. With a top-hat excitation, an experimental apparatus was developed for either a single thermal mirror or a single thermal lens measurement. Furthermore, the apparatus was used for concurrent measurements of thermal mirror and thermal lens. More physical properties could be measured using the concurrent measurements.

A composite photothermal technique for the measurement of thermal properties of solids

In this work, a composite photothermal technique combining open photoacoustic cell and photothermal deflection methods for thermal characterization of opaque solids was developed. An excitation laser was employed to concurrently generate both photoacoustic and mirage effects. Thermal diffusivity and thermal effusivity of carbon-based samples were measured, and the values of thermal conductivities and specific heat were then deduced. The experimental results were found to be in good agreement with the literature values. The photothermal technique developed in this work permits a convenient and precise measurement of thermal properties of solids.

Probe beam size effect on the measurement of the distance between the probe beam and the sample in photothermal deflection

A distance-scan method to determine the distance between the probe beam and sample, which is not easily measured exactly, in photothermal deflection (PD) was reported, with which the distance and thermal diffusivity of the deflecting medium can be simultaneously measured. Probe beam size effect (PBSE) on PD phase signal was quantitatively analyzed to clearly show its physical meaning. The measured distance was experimentally verified as correct and reliable, and the measured thermal diffusivities of N2 and CO2 are in good agreement with the literature values. They could not be precisely measured by phase signal without considering the PBSE.

Thermophysical property measurements using time-resolved photothermal deflection spectrometry with step optical excitation

This letter reports the theoretical and experimental results of thermophysical property measurements using our recently developed time-resolved photothermal deflection spectrometry (PDS) with step optical excitation. One-dimensional heat conduction boundary conditions of the third kind were derived, and a theoretical model with the boundary conditions was proposed. Both thermal diffusivity and effusivity of two well-known samples were precisely measured simultaneously by fitting experimental data to the theory. Thermal conductivity and unit volume specific heat then can be deduced. Moreover, time-resolved PDS with step optical excitation has the advantages of simpler experimental apparatus and less time consuming measurement, compared with the traditional periodically modulated PDS.

Note: Determination of effective gas diffusion coefficients of stainless steel films with differently shaped holes using a Loschmidt diffusion cell

In this work, an in-house made Loschmidt diffusion cell is used to measure the effective O(2)-N(2) diffusion coefficients through four porous samples of different simple pore structures. One-dimensional through-plane mass diffusion theory is applied to process the experimental data. It is found that both bulk diffusion coefficient and the effective gas diffusion coefficients of the samples can then be precisely determined, and the measured bulk one is in good agreement with the literature value. Numerical computation of three-dimensional mass diffusion through the samples is performed to calculate the effective gas diffusion coefficients. The comparison between the measured and calculated coefficient values shows that if the gas diffusion through a sample is dominated by one-dimensional diffusion, which is determined by the pore structure of the sample, these two values are consistent, and the sample can be used as a standard sample to test a gas diffusion measurement system.