Temperature Ramp Rate Research Articles

The effect of heteroatoms and temperature ramping rate on pyrolysis of coal tar pitch for high value of β-resin

The effect of heteroatoms and temperature ramping rate on pyrolysis of coal tar pitch for high value of β-resin

Development of a microfurnace dedicated to in situ scanning electron microscope observation up to 1300 °C. III. In situ high temperature experiments.

The FurnaSEM microfurnace was installed in the chamber of a scanning electron microscope to carry out in situ experiments at high temperatures and test its limits. The microfurnace was used in combination with different types of detectors (Everhart-Thornley for the collection of secondary electrons in a high vacuum, gas secondary electron detector for the specific collection of secondary electrons in the presence of gas, and Karmen© detector for the collection of backscattered electrons at high temperature). Experiments carried out on various samples (metal alloys and ceramics) show that the microfurnace operates in both high-vacuum and low-vacuum modes. Temperature ramp rates during temperature cycles applied to the sample range from 1 to 120 °C/min (temperature rise) and 1 to 480 °C/min (controlled and natural cooling). The maximum temperature at which images were recorded up to 25k × magnification was 1340 °C, with a residual air atmosphere of 120Pa. The choice of a flat furnace with the sample placed directly above it has enabled innovative experiments to be carried out, such as low-voltage imaging (using a shorter working distance-up to 10 mm-than is possible with conventional furnaces), 3D imaging (by tilting the stage by up to 10°), and high-temperature backscattered electron imaging (using a dedicated detector).

Combined laser-induced graphene and microcontact printing for processing scalable and stackable micro-stripe patterns toward multifunctional electronic devices

Laser-induced graphene (LIG) is a highly promising technology for assembling thin-film electronics with miniaturized surficial patterns, although hard to guarantee both high-quality formation of raw materials and high resolution of feature size. In this study, a combined microcontact printing (μCP) and LIG protocol is creatively utilized to fabricate ultra-thin graphene films with highly ordered micro-stripe arrays. In addition to realize various patterned structures with unique scalable and stackable characteristics, PAA concentration (4–8 wt%) is systematically investigated as a critical parameter to precisely control the feature size of micro-patterns before and after the irradiation process, including line width (before: 5.37–22.44 μm, after: 4.83–22.32 μm) and average height (before: 69.81–187.39 nm, after: 5.72–48.61 nm). By further exploring a defocused multi-lasing strategy, sheet resistance of the graphene array could be optimized dramatically from 634.1 kΩ/sq to 1.9 kΩ/sq, while maintaining low ablation (45.38 % porosity) and high carbon content (84.2 wt%). Lastly, the process is demonstrated to assemble different graphene based electronic devices with miniaturized sizes, including liquid sensors with sensitivity of 2.7 % μL−1 and electrothermal heaters with temperature-ramping rate as high as 24.7 °C/s and working temperature as high as 248 °C.

Deposition of high-quality, nanoscale SiO2 films and 3D structures

Silicon dioxide (SiO2) is ubiquitous in biomedical diagnostics and other applications as a capture medium for nucleic acids and proteins. Diagnostic devices have seen rapid miniaturisation in recent years, due to the increased demand for portable point-of-care diagnostics. However, there are increasing challenges with incorporating SiO2 nanostructures into diagnostic devices, due to the complexity of nanostructured SiO2 synthesis, often involving etching and chemical vapour deposition under high vacuum conditions.We report a novel and straightforward method for deposition of high-quality, nanoscale SiO2 films and 3D SiO2 structures using thermal decomposition of polydimethylsiloxane (PDMS), in a furnace at atmospheric pressure at 500 °C. This method allows individual nanometre controllability of conformal pinhole-free layers on a variety of materials and morphologies. The temperature ramp rate is a key factor in determining the SiO2 deposit morphology, with slower ramp rates leading to highly conformal 2D films and faster ones yielding 3D nanodentrite structures. For the 2D films, the film thickness, as determined by spectroscopic ellipsometry and confirmed by SEM data, is shown to correlate excellently with initial PDMS source material mass in the thickness range 0.8–18 nm. Fits to ellipsometry models confirm that the refractive index of the deposited film matches the expected value for SiO2, while electrical breakdown measurements confirm that the breakdown strength of the films is comparable to that of high-quality thermal oxides. Depositions on high aspect ratio ZnO nanostructures are shown to be highly conformal, leading to core-shell ZnO-SiO2 nanostructures whose shell thickness is in excellent agreement with the expected values from deposition on planar substrates. At faster ramp rates an abrupt morphological transition is seen to a deposit which displays a 3D nanodentrite morphology. The possibilities for applications of both morphologies (and core-shell combinations with other nanostructured materials) in biosensing and related areas are briefly discussed, and the DNA capture capabilities of each nanostructure are measured. The high aspect ratio nanodendrite structures allow for significant DNA capture within microfluidic devices in the presence of low DNA concentrations, with a maximum average capture efficiency of 43.4 % achieved in the presence of 10 ng/mL of DNA, which is an improvement by a factor of ∼ 3 over planar Si surfaces. Improvements by factors of >10 over planar surfaces were achieved at higher DNA concentrations of 100 and 1000 ng/mL.

In-situ investigation of the time-temperature dependent lattice and microstructure of Sn-Bi alloys

Alloys based on the Sn-Bi system are widely considered as the most promising candidates for low temperature solders (LTS) in the electronics industry due to their low liquidus temperature, non-toxicity and relatively low cost. However, implementation of LTS is complicated as they exhibit different characteristics from conventional Pb-free solders. While the solid solubility of alloying additions in Sn is typically <1 wt% in the current generation of Pb-free solders, the solubility of Bi in Sn ranges from less than 3 wt% at room temperature to 21 wt% at the eutectic temperature of 139 °C. In consequence, the microstructure and properties of Sn-Bi solders change significantly under varying temperature during normal service, affecting reliability. Since these changes are time and temperature dependent, interpreting results obtained using ex-situ methods requires assumptions about the stability of the alloy during transitions from the test environment to the observation environment, leading to an incomplete understanding of these changes. To address this, in-situ synchrotron powder X-ray diffraction (PXRD) and in-situ scanning electron microscopy (SEM) techniques were developed to investigate the time-temperature dependent lattice and microstructure of hypo-eutectic Sn-37wt%Bi and near-eutectic Sn-57wt%Bi solder alloys. This made possible for the first time the observation of changes during temperature fluctuations. The study revealed that lattice and microstructure are highly sensitive to factors like temperature ramp rate and isothermal holding time, not previously considered. The results will impact the design of electronic circuitry and process parameters during electronics assembly to enhance reliability and performance.

Transient testing of oxide fuels by spark plasma sintering and finite element analysis

In this paper, we report an innovative approach of using spark plasma sintering (SPS) combining with finite element modeling (FEM) to investigate the transient behavior of nuclear fuels. The temperature ramping rates of the SPS with special tooling can be controlled from 5 to 10 °C/s up to 500 °C/s, mimicking prototypical thermal profiles of the loss-of-coolant-accident (LOCA) and reactivity-induced-accident (RIA) events, respectively. The fresh UO2 pellets with micron grain size are synthesized by SPS. Their fracture and fragmentation behaviors are investigated under transient thermal testing, and temperature-gradient and thermal-stress are calculated by FEM. The micron-sized fresh UO2 displays good thermal shock stability and anti-cracking performance under the LOCA thermal test. Under simulated RIA conditions, the UO2 fuels crack due to the stress induced by the large thermal gradient. The unique capability of SPS with controlled temperature ramping enables a cost-effective approach for rapid screening and high throughput evaluation of nuclear fuels under power transients.

Sustainable production of hydrogen and carbon nanotubes/nanofibers from plastic waste through microwave degradation

Plastic waste pyrolysis to clean energy (H2) and valuable carbon nanotubes or nanofibers (CNTs/CNFs) is the most promising waste management and energy regeneration process. In this study, microwave-mediated single-step pyrolysis is used to produce COx-free hydrogen and CNTs/CNFs from real-world plastic films. Nickel, iron, and cobalt-based catalysts were prepared by the incipient wet-impregnation method and tested for real-world polyethylene plastic film degradation. In addition, the quality of CNTs produced and hydrogen yield were also compared for these catalysts. Various characterization tools were used to characterize the calcined catalysts, spent catalysts, and CNTs. Further, the effect of temperature ramp rate on hydrogen yield and CNTs properties was also analyzed. The results show that the iron-based catalyst produces a high yield of hydrogen and low-diameter and uniform-quality CNTs compared to other catalysts.

Retention Time Trajectory Matching for Peak Identification in Chromatographic Analysis.

Retention time drift caused by fluctuations in physical factors such as temperature ramping rate and carrier gas flow rate is ubiquitous in chromatographic measurements. Proper peak matching and identification across different chromatograms is critical prior to any subsequent analysis but is challenging without using mass spectrometry. The purpose of this work was to describe and validate a peak matching and identification method called retention time trajectory (RTT) matching that can be used in targeted analyses free of mass spectrometry. This method uses chromatographic retention times as the only input and identifies peaks associated with any subset of a predefined set of target compounds. An RTT is a two-dimensional (2D) curve formed uniquely by the retention times of the chromatographic peaks. The RTTs obtained from the chromatogram of a sample under test and those pre-installed in a library are matched and statistically compared. The best matched pair implies identification. Unlike most existing peak-alignment methods, no mathematical warping or transformation is involved. Based on the experimentally characterized RTT, an RTT hybridization method was also developed to rapidly generate more RTTs and expand the library without performing actual time-consuming chromatographic measurements, which enables successful peak matching even for chromatograms with severe retention time drifts. Additionally, 3.15 × 105 tests using experimentally obtained gas chromatograms and 2 × 1012 tests using two publicly available fruit metabolomics datasets validated the proposed method, demonstrating real-time peak/interferent identification.

Temperature Ramp Strategy for Regulating Oxygen Vacancies in NiCo2O4 Nanoneedles Towards Enhanced Electrocatalytic Water Splitting.

The oxide-based systems often suffer from higher overpotentials compared to transition metal sulphides and phosphides for the electrochemical hydrogen evolution reaction. Interestingly, the generation of oxygen vacancy has been seen as strategy for further activating transition metal oxides (NiCo2O4 as a model system) for electrochemical watersplitting. Herein, we employ the temperature ramp strategy (ambient air calcination) for the generation of oxygen vacancies in NiCo2O4 (NCO) towards tuning of electrocatalytic enhancements. The NiCo2O4 synthesized at temperature ramp rates of 2 (NCO-2), 5 (NCO-5), and 10ºC/ min (NCO-10) depicts contrasting structural features and varying Ni:Co:O surface composition. The decrease in the crystallite size and converse trend in the particle strain were observed from NCO-2 to NCO-10. Interestingly, the surface Ni:Co:O ratios of 1:0.78:3.6, 1:0.81:3.3, and 1:0.69:2.8 for NCO-2, NCO-5, and NCO-10, respectively, were observed. The reduced relative oxygen ratio in the latter implies generation of ample amount of oxygen vacancy defects. HER performance depicts a consistent trend with enhanced oxygen defect concentration with the overpotential requirement of 700, 647, and 597 mV for NCO-2, NCO-5, and NCO-10, respectively, for the generation of a cathodic current of 25 mA cm-2. The same trend in an electrocatalytic enhancement is observed for other cathodic currents.

A new approach to turbostratic carbon production via thermal salt-assisted treatment of graphite

Here graphite was found to undergo carbon/carbonate gasification at 800 °C, resulting in exfoliation of graphite to form turbostratic carbon. The lattice distance of graphene sheets in graphite are shown to undergo marked changes following treatment with molten ternary eutectic carbonate (Li2CO3: 43.5%, Na2CO3: 31.5%, K2CO3: 25%) during slow temperature ramping rates (5 °C/min) under N2 at temperatures above 750 °C. Initial findings suggest that approximately 50 wt% of graphite experiences interlayer expansion. The conventional d spacing of 0.34 nm is modified to a range of intervals between 0.41 nm and 1.22 nm. As a consequence of high operational temperature (800 °C), cations (Li+, Na+ and K+) as well as potentially the anion (CO32–) intercalate between graphitic layers and overcome Van der Waal force between layers. Employing a pressurized N2 environment of 5 bar and 10 bar successfully controls carbonate vaporization and decomposition, as well as inducing ordered layer manipulation to exfoliate more graphite planes from the edges towards deeper levels of the particles. Exploring parameters of both carbonate loading and treatment time in addition to pressure demonstrate that this work opens up a rich selection of parameters that can be used to produce carbons with tuned properties from graphite.

Characterization of the thermal death time landscape for Enchytraeus albidus

The influence of non-stressing temperatures on life-history traits of enchytraeids (e.g. growth and reproduction) is well described in the literature, but less is known about the influence of stressful temperatures, especially at the high end of the scale. In light of predicted climate changes, where the frequency and intensity of extreme weather events are increasing, it is important to provide detailed knowledge of the thermal limits of species. Experiments leading to a comprehensive understanding of species´ Thermal Death Time (TDT) landscape are particularly valuable because this allows modelling and predicting mortality under dynamic thermal scenarios. In static assays, we determined TDT50 of adult worms at a range of temperatures showing that 50% mortality (TDT50) was reached by exposure to 35.5 °C for only 6 min, whereas TDT50 at 31 °C was 257 min. By fitting the TDT curve to the measurements, we described the influence of temperature on the rate of injury accumulation leading to 50% mortality. Based on injury accumulation rates derived from static assays, we predicted the TDT50 in dynamic assays of various temperature ramping rates with high precision. Additional experiments showed that eggs and juveniles had the same sensitivity to high temperature as adult worms. Combined with previous research, our results show that E. albidus has a wide thermal niche in which survival is possible, from ca. − 25 to + 35 °C. However, exposure time is of the essence for surviving stressful temperatures in the high and low temperature ranges. We discuss that the wide thermal niche of E. albidus may partly explain how this species has become so widely distributed, from the temperate coastal climate in northern Spain to the high Arctic in Svalbard.

Investigating Fundamental Principles of Nonequilibrium Assembly Using Temperature-Sensitive Copolymers.

Both natural biomaterials and synthetic materials benefit from complex energy landscapes that provide the foundation for structure-function relationships and environmental sensitivity. Understanding these nonequilibrium dynamics is important for the development of design principles to harness this behavior. Using a model system of poly(ethylene glycol) methacrylate-based thermoresponsive lower critical solution temperature (LCST) copolymers, we explored the impact of composition and stimulus path on nonequilibrium thermal hysteretic behavior. Through turbidimetry analysis of nonsuperimposable heat-cool cycles, we observe that LCST copolymers show clear hysteresis that varies as a function of pendent side chain length and hydrophobicity. Hysteresis is further impacted by the temperature ramp rate, as insoluble states can be kinetically trapped under optimized temperature protocols. This systematic study brings to light fundamental principles that can enable the harnessing of out-of-equilibrium effects in synthetic soft materials.

In-situ investigation of solid phase evolution during lyophilization of mannitol-based antibody formulations using an XRPD climate chamber

Crystalline mannitol is commonly used as bulking agent in antibody formulations to provide structure to the lyophilized cake and prevent collapse. Depending on the lyophilization process conditions mannitol can either crystallize as α-, β-, δ-mannitol, mannitol-hemihydrate, or transition to its amorphous state. While crystalline mannitol helps to create a firmer cake structure this is not true for amorphous mannitol. The hemihydrate is also an undesired physical form as it may reduce the drug product stability by releasing bound water molecules into the cake. Our aim was to simulate lyophilization processes in an X-ray powder diffraction (XRPD) climate chamber. In the climate chamber, the process can be carried out fast with low sample quantities to determine optimal process conditions. Insights on the emergence of desired anhydrous mannitol forms helps to adjust the process parameters in larger scale freeze-dryers. In our study we have identified the critical process steps for our formulations and then varied relevant process parameters, which were the annealing temperature, annealing time and temperature ramp rate of the freeze-drying process. Furthermore, the effect of the presence of antibodies on excipient crystallization was investigated by performing the studies on placebo solutions versus two respective antibody formulations. A comparison of the products obtained in a freeze-dryer and the simulated process in the climate chamber showed good accordance demonstrating the method as suitable tool to identify ideal process conditions on a laboratory scale.

Gel-sol transition of thermoresponsive poly(vinyl alcohol) solution: Validation of the universal critical scaling relations

While undergoing gelation transition, a material passes through a distinctive state called the critical gel state. In the neighborhood of this critical gel state, how viscosity, equilibrium modulus, and relaxation times evolve are correlated by scaling relations, and their universality has been validated for materials undergoing the sol-gel transition. In this work, we extend this approach for the gel-sol transition of a thermoresponsive polymeric system of aqueous poly(vinyl alcohol) (PVOH) gel that passes through the critical state upon increasing temperature. We observe that, in the neighborhood of the critical gel state, the equilibrium modulus and viscosity demonstrate a power law dependence on the relative distance from the critical state in terms of normalized temperature. Furthermore, the relaxation times in the gel and the sol state shows symmetric power law divergence near the critical state. The corresponding critical power law exponents and the dynamic critical exponents computed at the critical gel-sol transition state validate the scaling and hyperscaling relations originally proposed for the critical sol-gel transition very well. Remarkably, the dependence of complex viscosity on frequency at different temperatures shows a comprehensive master curve irrespective of the temperature ramp rate independently in the gel and the sol state. This observation demonstrates how the shape of relaxation time spectrum is independent of both the temperature as well as the ramp rate. Since sol-gel and the gel-sol transitions are opposite to each other, the applicability of the scaling relations validated in this work suggests broader symmetry associated with how the structure evolves around the critical state irrespective of the direction.

Dynamic Electrification of Dry Reforming of Methane with In Situ Catalyst Regeneration

We report the design and performance of a rapid pulse Joule heating (RPH) reactor with an in situ Raman spectrometer for highly endothermic, reversible reactions. We demonstrate it for methane dry reforming over a bimetallic PtNi/SiO2 catalyst that shows better performance than its monometallic counterparts. The catalyst temperature ramp rate can reach ∼14000 °C/s, mainly owing to the low thermal mass and resistivity of the heating element. Joule heating elements afford temperatures unachievable by conventional technology to enhance performance and more than double the energy efficiency. Dynamic electrification can increase syngas productivity and rate. Extensive characterizations suggest that pulse heating creates an in situ catalyst regeneration strategy that suppresses coke formation, sintering, and phase segregation, resulting in improved catalyst stability, under many conditions. Potentially driven by renewable electricity, the RPH can provide superb process advantages for high-temperature endothermic reactions and lead to negative carbon emissions.

Activity and segregation behavior of Pd75%Ag25%(1 1 1) during CO oxidation – An in situ NAP-XPS investigation

The surface reactivity during CO oxidation over Pd(111) and Pd75%Ag25%(111) single crystals has been investigated using near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) under excess oxygen conditions (p ≈ 2 mbar, O2:CO=10). The (√6×√6) Pd5O4 surface oxide is present on Pd(111) when the surface is highly active under the applied conditions. The CO2 formation profile follows a hysteresis upon temperature cycling between 150 and 450 °C that depends on the temperature ramp rate. The behavior is different for Pd75%Ag25%(111), with the CO2 formation rate considerably lower, no surface oxide and only chemisorbed oxygen present at the surface at high temperature, reversible scrambling of the (near) surface Pd/(Pd+Ag) ratio, and no hysteresis behavior observed. The results suggest that the reactant activation is affected by both surface composition and surface termination, i.e. mechanistically different on Pd75%Ag25%(111) than Pd(111), and less efficient on (111) as compared to the (100) alloy counterpart.

Age differences in thermal comfort and physiological responses in thermal environments with temperature ramp

The well-being of the elderly is critical in today's aging society. However, the age difference in thermal comfort in buildings with unstable thermal environments is poorly understood. In this study, 32 gender-balanced elderly and young participants were recruited to investigate differences in thermal perceptions and physiological responses to thermal environments with temperature ramps between 34 °C and 18 °C (up and down) in a climate chamber. We found that the elderly have a time lag and smaller variation in thermal responses than the young group when air temperature changes, especially in non-neutral conditions. The elderly reported less thermal discomfort (P < 0.05) and fewer complaints of sick building syndrome (SBS) and perceived air quality (PAQ). Local thermal sensation vote (TSV) and local skin temperature (LST) results also revealed age differences in the coldest local body parts and TSV-LST relationships. The LST of the arms and head of the elderly was lower in some conditions, indicating that health risks should be considered more carefully. The elderly had significantly higher blood pressure and were more sensitive to temperature ramps than the young. Thermal perceptions and physiological responses were affected by both air temperature values and ramp direction. Linear regressions were performed to predict TSV as a function of PMV and temperature ramp rate ΔT for the elderly and young groups, respectively. Therefore, age should be considered when evaluating the thermal comfort of older adults in unstable environments.

Variation in Larval Thermal Tolerance of Three Saproxylic Beetle Species.

Temperature is a key abiotic condition that limits the distributions of organisms, and forest insects are particularly sensitive to thermal extremes. Whereas winged adult insects generally are able to escape unfavorable temperatures, other less-vagile insects (e.g., larvae) must withstand local microclimatic conditions to survive. Here, we measured the thermal tolerance of the larvae of three saproxylic beetle species that are common inhabitants of coarse woody debris (CWD) in temperate forests of eastern North America: Lucanus elaphus Fabricius (Lucanidae), Dendroides canadensis Latreille (Pyrochroidae), and Odontotaenius disjunctus Illiger (Passalidae). We determined how their critical thermal maxima (CTmax) vary with body size (mass), and measured the thermal profiles of CWD representing the range of microhabitats occupied by these species. Average CTmax differed among the three species and increased with mass intraspecifically. However, mass was not a good predictor of thermal tolerance among species. Temperature ramp rate and time in captivity also influenced larval CTmax, but only for D. canadensis and L. elaphus respectively. Heating profiles within relatively dry CWD sometimes exceeded the CTmax of the beetle larvae, and deeper portions of CWD were generally cooler. Interspecific differences in CTmax were not fully explained by microhabitat association, but the results suggest that the distribution of some species within a forest can be affected by local thermal extremes. Understanding the responses of saproxylic beetle larvae to warming habitats will help predict shifts in community structure and ecosystem functioning in light of climate change and increasing habitat fragmentation.

Thermal limits of Africanized honey bees are influenced by temperature ramping rate but not by other experimental conditions

Interest in assessing the critical thermal limits of bees is rapidly increasing, as these physiological traits are good predictors of bees' potential responses to extreme temperature changes, which is relevant in the context of global climate change. However, estimates of thermal limits may be influenced by several factors and published studies differ in experimental methods and conditions, such as the rate of temperature change (ramping rate) and feeding status, which might yield inaccurate predictions and limit comparisons across taxa and regions. Using Africanized honey bees as a model organism, we assessed the effect of ramping rate (0.25, 0.5, 0.75, 1.0 and 1.5 °C min−1) and length of starvation (recently fed vs. fasted for 6, 12, and 18 h) on foragers’ lower (CTMin) and upper (CTMax) thermal limits, as well as the effect of cold stress on CTMax. In addition, we evaluated the two approaches currently used to assess CTMax with a water bath: floating or submerging the testing vials in the bath. We found that critical thermal limits were influenced by ramping rates but not by the other assessed experimental conditions. On average, at ramping rates faster than 0.5 °C min−1, bees displayed a CTMin 1.1–2.6 °C lower and a CTMax 5.3–6.9 °C higher than those of the slowest ramping rate. We discuss the implications of these results and provide suggestions for future thermal studies on bees.

Thermal responses and skin temperature to moderate temperature ramps in winter: An office-lab study

In order to explore the acceptable temperature limits of humans in temperature ramps by intermittent heating in the north China, the research was conducted in an office-lab. Four indoor dynamic heating environments with different initial temperatures (15–18 °C) and change rates (0.02–0.18 °C/min) were created. The room temperature gradually rose as people entered the room and divided into two phases by the ramping rates, which was fast in the first phase. During the filed experiments, the variations of overall and local thermal responses were investigated while environmental parameters was monitored. Additionally, the local skin temperatures of participants' hand and ankle were also recorded.The results indicated that the variations of skin temperature from different exposed parts were different. It indicated that humans can make active physiological adjustments according to environmental changes. Moreover, the subject's thermal responses were lagging and affected by the thermal experience. The thermal sensation vote (TSV) was statistically different between the two phases. The calf was the most significant factor on the overall thermal sensation. Furthermore, the TSV significantly affected other psychological responses. The relationships between the TSV and other thermal responses were observed. The thermal sensation evaluation models were established.In summary, the indoor temperature of 16–18 °C is recommended as the initial temperature when the temperature ramping rate is less than 0.2 °C/min. This study gives a theoretical guide for the creation of dynamic indoor thermal environments, which is beneficial for thermal comfort, health, and energy saving.