Temperature-dependent complex dielectric permittivity: a simple measurement strategy for liquid-phase samples.

Microwaves (MWs) are an emerging technology for intensified and electrified chemical manufacturing. MW heating is intimately linked to a material's dielectric permittivity. These properties are highly dependent on temperature and pressure, but such datasets are not readily available due to the limited accessibility of the current methodologies to process-oriented laboratories. We introduce a simple, benchtop approach for producing these datasets near the 2.45 GHz industrial, medical, and scientific (ISM) frequency for liquid samples. By building upon a previously-demonstrated bireentrant microwave measurement cavity, we introduce larger pressure- and temperature-capable vials to deduce temperature-dependent permittivity quickly and accurately for vapor pressures up to 7 bar. Our methodology is validated using literature data, demonstrating broad applicability for materials with dielectric constant ε' ranging from 1 to 100. We provide new permittivity data for water, organic solvents, and hydrochloric acid solutions. Finally, we provide simple fits to our data for easy use.

Microwave-assisted, performance-advantaged electrification of propane dehydrogenation.

Nonoxidative propane dehydrogenation (PDH) produces on-site propylene for value-added chemicals. While commercial, its modest selectivity and catalyst deactivation hamper the process efficiency and limit operation to lower temperatures. We demonstrate PDH in a microwave (MW)-heated reactor over PtSn/SiO2 catalyst pellets loaded in a SiC monolith acting as MW susceptor and a heat distributor while ensuring comparable conditions with conventional reactors. Time-on-stream experiments show active and stable operation at 500°C without hydrogen addition. Upon increasing temperature or feed partial pressure at high space velocity, catalysts under MWs show resistance in coking and sintering, high activity, and selectivity, starkly contrasting conventional reactors whose catalyst undergoes deactivation. Mechanistic differences in coke formation are exposed. Gas-solid temperature gradients are computationally investigated, and nanoscale temperature inhomogeneities are proposed to rationalize the different performances of the heating modes. The approach highlights the great potential of electrification of endothermic catalytic reactions.

Evaluation of Microwave Synthesis of Ceramic Pigments Based on In Situ Dielectric Characterization.

The application of microwave technology for efficient and environmentally friendly synthesis of ceramic pigments is a successful and rapidly evolving area of research. However, a clear understanding of the reactions and their relationship with the material absorbance has not been fully achieved. The present study introduces an in situ permittivity characterization technique, which serves as an innovative and precise tool for assessing the microwave synthesis of ceramic pigments. Several processing parameters (atmosphere, the heating rate, raw mixture composition and particle size) were evaluated by studying the permittivity curves as a function of temperature to elucidate their effect on the synthesis temperature and the final pigment quality. The validity of the proposed approach was verified through correlation with other well-known analysis techniques, such as DSC or XRD, providing valuable information about the reaction mechanisms and the optimum conditions for the synthesis process. In particular, changes in permittivity curves were linked, for the first time, to undesired metal oxide reduction at too-high heating rates and could be used to detect pigment synthesis failures and ensure product quality. The proposed dielectric analysis was also found to be a useful tool for optimizing raw material composition for the microwave process, including the use of chromium with lower specific surface area and flux removal.

High-Resolution Detection of Rock-Forming Minerals by Permittivity Measurements with a Near-Field Scanning Microwave Microscope.

The identification of the minerals composing rocks and their dielectric characterization is essential for the utilization of microwave energy in the rock industry. This paper describes the use of a near-field scanning microwave microscope with enhanced sensitivity for non-invasive measurements of permittivity maps of rock specimens at the micrometer scale in non-contact mode. The microwave system comprises a near-field probe, an in-house single-port vectorial reflectometer, and all circuitry and software needed to make a stand-alone, portable instrument. The relationship between the resonance parameters of the near-field probe and the dielectric properties of materials was determined by a combination of classical cavity perturbation theory and an image charge model. The accuracy of this approach was validated by a comparison study with reference materials. The device was employed to determine the permittivity maps of a couple of igneous rock specimens with low-loss and high-loss minerals. The dielectric results were correlated with the minerals comprising the samples and compared with the dielectric results reported in the literature, with excellent agreements.

Detection of Anti-Counterfeiting Markers through Permittivity Maps Using a Micrometer Scale near Field Scanning Microwave Microscope.

This paper describes the use of microwave technology to identify anti-counterfeiting markers on banknotes. The proposed method is based on a robust near-field scanning microwave microscope specially developed to measure permittivity maps of heterogeneous paper specimens at the micrometer scale. The equipment has a built-in vector network analyzer to measure the reflection response of a near-field coaxial probe, which makes it a standalone and portable device. A new approach employing the information of a displacement laser and the cavity perturbation technique was used to determine the relationship between the dielectric properties of the specimens and the resonance response of the probe, avoiding the use of distance-following techniques. The accuracy of the dielectric measurements was evaluated through a comparative study with other well-established cavity methods, revealing uncertainties lower than 5%, very similar to the accuracy reported by other more sophisticated setups. The device was employed to determine the dielectric map of a watermark on a 20 EUR banknote. In addition, the penetration capabilities of microwave energy allowed for the detection of the watermark when concealed behind dielectric or metallic layers. This work demonstrates the benefits of this microwave technique as a novel method for identifying anti-counterfeiting features, which opens new perspectives with which to develop optically opaque markers only traceable through this microwave technique.

Evidence of a new phase in gypsum-anhydrite transformations under microwave heating by in situ dielectric analysis and Raman spectroscopy.

Mineral transformations of the gypsum-anhydrite system under microwave heating have been studied using in situ dielectric thermal analysis (MW-DETA) and Raman spectroscopy simultaneously. The dielectric properties of samples that were measured under microwave heating provided thorough information about the dynamics of the gypsum-anhydrite system transformations and its significance from the mineralogical point of view. In particular, the MW-DETA technique revealed a new intermediate phase with a γ-anhydrite structure. This phase corresponds to the soluble stage of γ-anhydrite, and it is characterized by a high ionic charge inside the crystal channels. The complete sequence is gypsum → 0.625-subhydrate → bassanite → hydro γ-anhydrite → anhydrous γ-anhydrite → ß-anhydrite. The transformations were also assessed using DSC, TG, DTA and dielectric measurements at room temperature, as well as other techniques including X-ray powder diffraction (XRPD) and high-temperature XRD (HT-XRD). Correlations between the dielectric properties with temperature and the rest of the techniques elucidated the heating mechanisms of this material under microwave energy during the different stages. The in situ combination of the MW-DETA and the Raman analysis appears to be a powerful technique, providing new insights about the mechanisms which govern the volumetric heating of this and other materials.

In Situ Monitoring of Microwave Processing of Materials at High Temperatures through Dielectric Properties Measurement.

Microwave-assisted processes have recognized advantages over more conventional heating techniques. However, the effects on the materials' microstructure are still a matter of study, due to the complexity of the interaction between microwaves and matter, especially at high temperatures. Recently developed advanced microwave instrumentation allows the study of high temperature microwave heating processes in a way that was not possible before. In this paper, different materials and thermal processes induced by microwaves have been studied through the in situ characterization of their dielectric properties with temperature. This knowledge is crucial in several aspects: to analyze the effects of the microwave field on the reaction pathways; to design and optimize microwave-assisted processes, and to predict the behavior of materials leading to repeatable and reliable heating processes, etc.

Non-invasive and continuous monitoring of the sol-gel phase transition of supramolecular gels using a fast (open-ended coaxial) microwave sensor.

An open coaxial re-entrant microwave sensor has been used for the non-invasive and continuous monitoring of the sol-gel transition of physical gels characterized by different gelation mechanisms, solvents, compositions, and stabilities. Comparison of measurements by differential scanning calorimetry allowed the identification of the phase transition by a change in the dielectric properties of the material over time.

Modeling microwave power structures based on k-furcated waveguides arbitrarily filled with materials by modal techniques.

Waveguide structures are very popular in the microwave power industry due to their power handling capabilities. Modal expansion of the waveguide fields and application of the circuit theory allow for the division of a complex device into several simpler sections which can be analyzed separately with the best suited method. The modal techniques can be divided into two groups--those which analyze junctions or discontinuities and those which examine propagation characteristics. In this paper, a review of modal techniques for high power applications is given. Modal expansion of the fields in the waveguides is then performed and applied to modeling of k-furcated waveguides. The modal analysis based on the Coupled Mode Method is described for the waveguides partially filled with isotropic materials. A hybrid modal analysis coupled with Finite Element Method suitable for more complex waveguide structures is also described. Computational results obtained for some real-life microwave devices are presented. Excellent agreement was found when comparing the results with those generated with a commercial FDTD simulator demonstrates the validity and reliability of the proposed method.