Wireless Passive Ceramic Sensor for Far-Field Temperature Measurement at High Temperatures.

A passive wireless high-temperature sensor for far-field applications was developed for stable temperature sensing up to 1000 °C. The goal is to leverage the properties of electroceramic materials, including adequate electrical conductivity, high-temperature resilience, and chemical stability in harsh environments. Initial sensors were fabricated using Ag for operation to 600 °C to achieve a baseline understanding of temperature sensing principles using patch antenna designs. Fabrication then followed with higher temperature sensors made from (In, Sn) O2 (ITO) for evaluation up to 1000 °C. A patch antenna was modeled in ANSYS HFSS to operate in a high-frequency region (2.5-3.5 GHz) within a 50 × 50 mm2 confined geometric area using characteristic material properties. The sensor was fabricated on Al2O3 using screen printing methods and then sintered at 700 °C for Ag and 1200 °C for ITO in an ambient atmosphere. Sensors were evaluated at 600 °C for Ag and 1000 °C for ITO and analyzed at set interrogating distances up to 0.75 m using ultra-wideband slot antennas to collect scattering parameters. The sensitivity (average change in resonant frequency with respect to temperature) from 50 to 1000 °C was between 22 and 62 kHz/°C which decreased as interrogating distances reached 0.75 m.

Coaxial Ceramic Direct Ink Writing on Heterogenous and Rough Surfaces: Investigation of Core-Shell Interactions.

In this work, coaxial conductor-ceramic direct ink writing enables the printing of sensitive or encapsulated materials onto heterogeneous and rough substrates. While encasing the core fluid within a stiff ceramic shell, continuity may be maintained, even while printing onto conventionally challenging substrates. Here, we report the development of a coaxial ceramic direct ink writing suite and explore coflow interrelationships based on microfluidic principles. A coaxial nozzle is designed to facilitate the coextrusion of an alumina shell, whereas indium-tin-oxide inks constitute the core. In this manner, a core-shell ceramic element may be printed onto rough substrates for future high-temperature applications. Colloidal inks are engineered to provide the required rheological and sintering performance. Moreover, flow simulations in conjunction with microfluidic coflow principles are used to explore the coaxial printing processing space, thus controlling the core-shell architectures. Physical modeling is further used to analyze core deformations and eccentricity. Simulations are validated experimentally, and the analyses are used to deposit coaxial ceramic features onto heterogeneous, high-temperature ceramic substrates.

All-Ceramic Passive Wireless Temperature Sensor Realized by Tin-Doped Indium Oxide (ITO) Electrodes for Harsh Environment Applications.

In this work, an all-ceramic passive wireless inductor-capacitor (LC) resonator was presented for stable temperature sensing up to 1200 °C in air. Instead of using conventional metallic electrodes, the LC resonators are modeled and fabricated with thermally stable and highly electroconductive ceramic oxide. The LC resonator was modeled in ANSYS HFSS to operate in a low-frequency region (50 MHz) within 50 × 50 mm geometry using the actual material properties of the circuit elements. The LC resonator was composed of a parallel plate capacitor coupled with a planar inductor deposited on an Al2O3 substrate using screen-printing, and the ceramic pattern was sintered at 1250 °C for 4 h in an ambient atmosphere. The sensitivity (average change in resonant frequency with respect to temperature) from 200-1200 °C was ~170 kHz/°C. The temperature-dependent electrical conductivity of the tin-doped indium oxide (ITO, 10% SnO2 doping) on the quality factor showed an increase of Qf from 36 to 43 between 200 °C and 1200 °C. The proposed ITO electrodes displayed improved sensitivity and quality factor at elevated temperatures, proving them to be an excellent candidate for temperature sensing in harsh environments. The microstructural analysis of the co-sintered LC resonator was performed using a scanning electron microscope (SEM) which showed that there are no cross-sectional and topographical defects after several thermal treatments.

Fabrication and Thermoelectric Characterization of Transition Metal Silicide-Based Composite Thermocouples.

Metal silicide-based thermocouples were fabricated by screen printing thick films of the powder compositions onto alumina tapes followed by lamination and sintering processes. The legs of the embedded thermocouples were composed of composite compositions consisting of MoSi2, WSi2, ZrSi2, or TaSi2 with an additional 10 vol % Al2O3 to form a silicide⁻oxide composite. The structural and high-temperature thermoelectric properties of the composite thermocouples were examined using X-ray diffraction, scanning electron microscopy and a typical hot⁻cold junction measurement technique. MoSi2-Al2O3 and WSi2-Al2O3 composites exhibited higher intrinsic Seebeck coefficients (22.2⁻30.0 µV/K) at high-temperature gradients, which were calculated from the thermoelectric data of composite//Pt thermocouples. The composite thermocouples generated a thermoelectric voltage up to 16.0 mV at high-temperature gradients. The MoSi2-Al2O3//TaSi2-Al2O3 thermocouple displayed a better performance at high temperatures. The Seebeck coefficients of composite thermocouples were found to range between 20.9 and 73.0 µV/K at a temperature gradient of 1000 °C. There was a significant difference between the calculated and measured Seebeck coefficients of these thermocouples, which indicated the significant influence of secondary silicide phases (e.g., Mo5Si3, Ta5Si3) and possible local compositional changes on the overall thermoelectric response. The thermoelectric performance, high sensitivity, and cost efficiency of metal silicide⁻alumina ceramic composite thermocouples showed promise for high-temperature and harsh-environment sensing applications.

Determination of a homogeneity factor for composite materials by a microstructural image analysis method.

The physical properties of particle-reinforced composite materials are highly affected by the distribution of particles within a matrix material. In this study, a microstructural image analysis method with a new distribution index for quantifying the degree of distribution in composite materials was developed. The free-path spacing between particles was measured to calculate the distribution (D) index based on the coefficient of variation. The proposed method was applied to six digitally created reference patterns as representative binary composite microstructures and three actual ceramic-matrix composites, respectively. It is found that the D index increased from 0.00 to 0.67 depending on the degree of distribution or homogeneity level based on the reference patterns. The homogeneity levels for the binary composites are then classified from a perfect (maximum) to very low level (minimum) based on increasing D index values, where a high D index presents a poorer distribution. The results obtained for reference patterns and metal silicide-refractory oxide composite microstructures indicate that the proposed method is a useful tool to quantify the degree of distribution with high accuracy, and can be efficiently used for different types of composite microstructures.

Evaluation of the effect of valence state on cerium oxide nanoparticle toxicity following intratracheal instillation in rats.

Cerium (Ce) is becoming a popular metal for use in electrochemical applications. When in the form of cerium oxide (CeO2), Ce can exist in both 3 + and 4 + valence states, acting as an ideal catalyst. Previous in vitro and in vivo evidence have demonstrated that CeO2 has either anti- or pro-oxidant properties, possibly due to the ability of the nanoparticles to transition between valence states. Therefore, we chose to chemically modify the nanoparticles to shift the valence state toward 3+. During the hydrothermal synthesis process, 10 mol% gadolinium (Gd) and 20 mol% Gd, were substituted into the lattice of the CeO2 nanoparticles forming a perfect solid solution with various A-site valence states. These two Gd-doped CeO2 nanoparticles were compared to pure CeO2 nanoparticles. Preliminary characteristics indicated that doping results in minimal size and zeta potential changes but alters valence state. Following characterization, male Sprague-Dawley rats were exposed to 0.5 or 1.0 mg/kg nanoparticles via a single intratracheal instillation. Animals were sacrificed and bronchoalveolar lavage fluid and various tissues were collected to determine the effect of valence state and oxygen vacancies on toxicity 1-, 7-, or 84-day post-exposure. Results indicate that damage, as measured by elevations in lactate dehydrogenase, occurred within 1-day post-exposure and was sustained 7-day post-exposure, but subsided to control levels 84-day post-exposure. Furthermore, no inflammatory signaling or lipid peroxidation occurred following exposure with any of the nanoparticles. Our results implicate that valence state has a minimal effect on CeO2 nanoparticle toxicity in vivo.

Cerium Dioxide Nanoparticle Exposure Improves Microvascular Dysfunction and Reduces Oxidative Stress in Spontaneously Hypertensive Rats.

The elevated production of reactive oxygen species (ROS) in the vascular wall is associated with cardiovascular diseases such as hypertension. This increase in oxidative stress contributes to various mechanisms of vascular dysfunction, such as decreased nitric oxide bioavailability. Therefore, anti-oxidants are being researched to decrease the high levels of ROS, which could improve the microvascular dysfunction associated with various cardiovascular diseases. From a therapeutic perspective, cerium dioxide nanoparticles (CeO2 NP) hold great anti-oxidant potential, but their in vivo activity is unclear. Due to this potential anti-oxidant action, we hypothesize that injected CeO2 NP would decrease microvascular dysfunction and oxidative stress associated with hypertension. In order to simulate a therapeutic application, spontaneously hypertensive (SH) and Wistar-Kyoto (WKY) rats were intravenously injected with either saline or CeO2 NP (100 µg suspended in saline). Twenty-four hours post-exposure mesenteric arteriolar reactivity was assessed via intravital microscopy. Endothelium-dependent and -independent function was assessed via acetylcholine and sodium nitroprusside. Microvascular oxidative stress was analyzed using fluorescent staining in isolated mesenteric arterioles. Finally, systemic inflammation was examined using a multiplex analysis and venular leukocyte flux was counted. Endothelium-dependent dilation was significantly decreased in the SH rats (29.68 ± 3.28%, maximal response) and this microvascular dysfunction was significantly improved following CeO2 NP exposure (43.76 ± 4.33%, maximal response). There was also an increase in oxidative stress in the SH rats, which was abolished following CeO2 NP treatment. These results provided evidence that CeO2 NP act as an anti-oxidant in vivo. There were also changes in the inflammatory profile in the WKY and SH rats. In WKY rats, IL-10 and TNF-α were increased following CeO2 NP treatment. Finally, leukocyte flux was increased in the SH rats (34 ± 4 vs. 17 ± 3 cells/min in the normotensive controls), but this activation was decreased following exposure (15 ± 2 vs. 34 ± 4 cells/min). These results indicated that CeO2 NP may alter the inflammatory response in both SH and WKY rats. Taken together, these results provide evidence that CeO2 NP act as an anti-oxidant in vivo and may improve microvascular reactivity in a model of hypertension.

The Effect of Cerium Oxide Nanoparticle Valence State on Reactive Oxygen Species and Toxicity.

Cerium oxide (CeO2) nanoparticles, which are used in a variety of products including solar cells, gas sensors, and catalysts, are expected to increase in industrial use. This will subsequently lead to additional occupational exposures, making toxicology screenings crucial. Previous toxicology studies have presented conflicting results as to the extent of CeO2 toxicity, which is hypothesized to be due to the ability of Ce to exist in both a +3 and +4 valence state. Thus, to study whether valence state and oxygen vacancy concentration are important in CeO2 toxicity, CeO2 nanoparticles were doped with gadolinium to adjust the cation (Ce, Gd) and anion (O) defect states. The hypothesis that doping would increase toxicity and decrease antioxidant abilities as a result of increased oxygen vacancies and inhibition of +3 to +4 transition was tested. Differences in toxicity and reactivity based on valence state were determined in RLE-6TN rat alveolar epithelial and NR8383 rat alveolar macrophage cells using enhanced dark field microscopy, electron paramagnetic resonance (EPR), and annexin V/propidium iodide cell viability stain. Results from EPR indicated that as doping increased, antioxidant potential decreased. Alternatively, doping had no effect on toxicity at 24 h. The present results imply that as doping increases, thus subsequently increasing the Ce(3+)/Ce(4+) ratio, antioxidant potential decreases, suggesting that differences in reactivity of CeO2 are due to the ability of Ce to transition between the two valence states and the presence of increased oxygen vacancies, rather than dependent on a specific valence state.

Intravenous and gastric cerium dioxide nanoparticle exposure disrupts microvascular smooth muscle signaling.

Cerium dioxide nanoparticles (CeO2 NP) hold great therapeutic potential, but the in vivo effects of non-pulmonary exposure routes are unclear. The first aim was to determine whether microvascular function is impaired after intravenous and gastric CeO2 NP exposure. The second aim was to investigate the mechanism(s) of action underlying microvascular dysfunction following CeO2 NP exposure. Rats were exposed to CeO2 NP (primary diameter: 4 ± 1 nm, surface area: 81.36 m(2)/g) by intratracheal instillation, intravenous injection, or gastric gavage. Mesenteric arterioles were harvested 24 h post-exposure and vascular function was assessed using an isolated arteriole preparation. Endothelium-dependent and independent function and vascular smooth muscle (VSM) signaling (soluble guanylyl cyclase [sGC] and cyclic guanosine monophosphate [cGMP]) were assessed. Reactive oxygen species (ROS) generation and nitric oxide (NO) production were analyzed. Compared with controls, endothelium-dependent and independent dilation were impaired following intravenous injection (by 61% and 45%) and gastric gavage (by 63% and 49%). However, intravenous injection resulted in greater microvascular impairment (16% and 35%) compared with gastric gavage at an identical dose (100 µg). Furthermore, sGC activation and cGMP responsiveness were impaired following pulmonary, intravenous, and gastric CeO2 NP treatment. Finally, nanoparticle exposure resulted in route-dependent, increased ROS generation and decreased NO production. These results indicate that CeO2 NP exposure route differentially impairs microvascular function, which may be mechanistically linked to decreased NO production and subsequent VSM signaling. Fully understanding the mechanisms behind CeO2 NP in vivo effects is a critical step in the continued therapeutic development of this nanoparticle.

Pulmonary cerium dioxide nanoparticle exposure differentially impairs coronary and mesenteric arteriolar reactivity.

Cerium dioxide nanoparticles (CeO2 NPs) are an engineered nanomaterial (ENM) that possesses unique catalytic, oxidative, and reductive properties. Currently, CeO2 NPs are being used as a fuel catalyst but these properties are also utilized in the development of potential drug treatments for radiation and stroke protection. These uses of CeO2 NPs present a risk for human exposure; however, to date, no studies have investigated the effects of CeO2 NPs on the microcirculation following pulmonary exposure. Previous studies in our laboratory with other nanomaterials have shown impairments in normal microvascular function after pulmonary exposures. Therefore, we predicted that CeO2 NP exposure would cause microvascular dysfunction that is dependent on the tissue bed and dose. Twenty-four-hour post-exposure to CeO2 NPs (0-400 µg), mesenteric, and coronary arterioles was isolated and microvascular function was assessed. Our results provided evidence that pulmonary CeO2 NP exposure impairs endothelium-dependent and endothelium-independent arteriolar dilation in a dose-dependent manner. The CeO2 NP exposure dose which causes a 50 % impairment in arteriolar function (EC50) was calculated and ranged from 15 to 100 µg depending on the chemical agonist and microvascular bed. Microvascular assessments with acetylcholine revealed a 33-75 % reduction in function following exposure. Additionally, there was a greater sensitivity to CeO2 NP exposure in the mesenteric microvasculature due to the 40 % decrease in the calculated EC50 compared to the coronary microvasculature EC50. CeO2 NP exposure increased mean arterial pressure in some groups. Taken together, these observed microvascular changes may likely have detrimental effects on local blood flow regulation and contribute to cardiovascular dysfunction associated with particle exposure.