A thermal-gradient approach to variable-temperature measurements resolved in space
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99 GENERAL AND MISCELLANEOUS↗
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Upper critical solution temperature polymer assemblies via variable temperature liquid phase transmission electron microscopy and liquid resonant soft X-ray scattering
Abstract Here, we study the upper critical solution temperature triggered phase transition of thermally responsive poly(ethylene glycol)- block -poly(ethylene glycol) methyl ether acrylate- co -poly(ethylene glycol) phenyl ether acrylate- block -polystyrene nanoassemblies in isopropanol. To gain mechanistic insight into the organic solution-phase dynamics of the upper critical solution temperature polymer, we leverage variable temperature liquid-cell transmission electron microscopy correlated with variable temperature liquid resonant soft X-ray scattering. Heating above the upper critical solution temperature triggers a reduction in particle size and a morphological transition from a spherical core shell particle with a complex, multiphase core to a micelle with a uniform core and Gaussian polymer chains attached to the surface. These correlated solution phase methods, coupled with mass spectral validation and modeling, provide unique insight into these thermoresponsive materials. Moreover, we detail a generalizable workflow for studying complex, solution-phase nanomaterials via correlative methods.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Phase Transitions in Metal–Organic Frameworks Directly Monitored through In Situ Variable Temperature Liquid-Cell Transmission Electron Microscopy and In Situ X-ray Diffraction
Zr 6 -based metal–organic frameworks (MOFs) with tetratopic organic linkers have been extensively investigated owing to their versatile structural tunability. While diverse topologies and polymorphism in the resulting MOFs are often encountered with tetratopic linkers and Zr 6 nodes, reports on phase transitions within these systems are rare. Thus, we have a limited understanding of polymorph transformations, hindering the rational development of pure phase materials. In this study, a phase transition from a microporous MOF, scu-NU-906, to a mesoporous MOF, csq-NU-1008, was discovered and monitored through in situ variable temperature liquid-cell transmission electron microscopy (VT-LCTEM), high-resolution transmission electron microscopy (HRTEM), and in situ variable temperature powder X-ray diffraction (VT-PXRD). Furthermore, it was found that the microporous- to-mesoporous transformation in the presence of formic acid occurs via a concomitant dissolution–reprecipitation process.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Thermoelectrically-cooled variable-temperature probe
Variable-temperature probe for electron spectroscopy requires no cryogenic liquids or resistance heating elements. Device consists of heat sink, probe tip, and nickel-plated copper body which resists oxidation and transfers heat efficiently between tip and heat sink.
Kelso, R. M.↗
The Role of Land‐Atmosphere Feedbacks in Midlatitude Wintertime Surface Temperature Variability
Accurately representing synoptic near-surface temperature variability is crucial to predict weather extremes, yet models remain biased. Existing studies primarily attribute wintertime midlatitude near-surface temperature variability to tropospheric large-scale advection, assuming minimal land influence. However, nudging the model's circulation toward observations yields little improvement in wintertime temperature variance over Northern Hemisphere land, suggesting that land-atmosphere interactions also warrant attention. We introduce a new scaling framework for temperature variance that incorporates local land-atmosphere feedbacks. Comparing our framework to the mixing length approach—which links temperature variance to the meridional temperature gradient and air parcel displacement (mixing length)—shows that land-atmosphere feedbacks are inherently embedded in the mixing length, a connection previously overlooked. Roles of land–atmosphere feedbacks are evaluated via model experiments with perturbed circulation, land, or both. We find that longwave radiative damping dominates temperature variance responses over meridional temperature gradient when both land and circulation are perturbed.
atmosheric science↗
Temperature Variability Associated with the Middle Atmosphere Electrodynamics (MAE-1) Campaign
Meteorological rockets launched during the Middle Atmosphere Electrodynamics (MAE-1) Campaign in October 1980 from Andoya Rocket Range (ARR), Norway, exhibited large and unexpected temperature variability. Temperatures were found to vary as much as 20 C within a few hours and demonstrated a similar type of variability from one day to the next. Following examination of the reduced rocketsonde profiles the question was raised whether the observed variability was due to natural atmospheric variability or instrument malfunction. Small-scale variability, as observed, may result from one or multiple sources, e.g., intense storms upstream from the observing site, orography such as mountain waves off of the Greenland Plateau, convective activity, gravity waves, etc. Arranging the observations spaced over time showed that the perturbations moved downward. Prior to MAE-1 very few small rocketsonde measurements had been launched from ARR, thus the quality of the initial measurements in early October caused concern when the large variability was noted. We discuss the errors of the rocketsonde measurements, graphically review the nature of the variability observed, compare the data with other measurements, and postulate a possible cause for the variability.
Schmidlin, F. J.↗
The role of blocking circulation and emerging open water feedbacks on Greenland cold‐season air temperature variability over the last century
Substantial marine, terrestrial, and atmospheric changes have occurred over the Greenland region during the last century. Several studies have documented record‐levels of Greenland Ice Sheet (GrIS) summer melt extent during the 2000s and 2010s, but relatively little work has been carried out to assess regional climatic changes in other seasons. Here, we focus on the less studied cold‐season (i.e., autumn and winter) climate, tracing the long‐term (1873–2013) variability of Greenland's air temperatures through analyses of coastal observations and model‐derived outlet glacier series and their linkages with North Atlantic sea ice, sea surface temperature (SST), and atmospheric circulation indices. Through a statistical framework, large amounts of west and south Greenland temperature variance (up to r^2~50%) can be explained by the seasonally‐contemporaneous combination of the Greenland Blocking Index (GBI) and the North Atlantic Oscillation (NAO; hereafter the combination of GBI and NAO is termed GBI). Lagged and concomitant regional sea‐ice concentration (SIC) and the Atlantic Multidecadal Oscillation (AMO) seasonal indices account for small amounts of residual air temperature variance (r^2<~10%) relative to the GBI. The correlations between GBI and cold‐season temperatures are predominantly positive and statistically‐significant through time, while regional SIC conditions emerge as a significant covariate from the mid‐20th century through the conclusion of the study period. The inclusion of the cold‐season Pacific Decadal Oscillation (PDO) in multivariate analyses bolsters the air temperature variance explained by the North Atlantic regional predictors, suggesting the remote, background climate state is important to long‐term Greenland temperature variability. These findings imply that large‐scale tropospheric circulation has a strong control on surface temperature over Greenland through dynamic and thermodynamic impacts and stress the importance of understanding the evolving two‐way linkages between the North Atlantic marine and atmospheric environment in order to more accurately predict Greenland seasonal climate variability and change through the 21st century.
air temperatures↗
Variable Temperature Behaviour of the Hybrid Double Perovskite MA 2 KBiCl 6
Perovskite-related materials show very promising properties in many fields. Pb-free perovskites are particularly interesting, because of the toxicity of Pb. In this study, hybrid double perovskite MA 2 KBiCl 6 (MA = methylammonium cation) was found to have interesting variable temperature behaviours. Both variable temperature single crystal X-ray diffraction, synchrotron powder diffraction, and Raman spectroscopy were conducted to reveal a rhombohedral to cubic phase transition at around 330 K and an order to disorder transition for inorganic cage below 210 K.
36 MATERIALS SCIENCE↗
Thermoresponsive polymer assemblies via variable temperature liquid-phase transmission electron microscopy and small angle X-ray scattering
Abstract Herein, phase transitions of a class of thermally-responsive polymers, namely a homopolymer, diblock, and triblock copolymer, were studied to gain mechanistic insight into nanoscale assembly dynamics via variable temperature liquid-cell transmission electron microscopy (VT-LCTEM) correlated with variable temperature small angle X-ray scattering (VT-SAXS). We study thermoresponsive poly(diethylene glycol methyl ether methacrylate) (PDEGMA)-based block copolymers and mitigate sample damage by screening electron flux and solvent conditions during LCTEM and by evaluating polymer survival via post-mortem matrix-assisted laser desorption/ionization imaging mass spectrometry (MALDI-IMS). Our multimodal approach, utilizing VT-LCTEM with MS validation and VT-SAXS, is generalizable across polymeric systems and can be used to directly image solvated nanoscale structures and thermally-induced transitions. Our strategy of correlating VT-SAXS with VT-LCTEM provided direct insight into transient nanoscale intermediates formed during the thermally-triggered morphological transformation of a PDEGMA-based triblock. Notably, we observed the temperature-triggered formation and slow relaxation of core-shell particles with complex microphase separation in the core by both VT-SAXS and VT-LCTEM.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Feasibility investigation of a low-temperature, variable infrared source. Horizon definition study
Feasibility of low temperature, variable infrared source - calibration of instrumentation used in defining earth horizon
Schmidt, R. N.↗
Variable-Temperature Cryostat For Radiation-Damage Testing Of Germanium Detectors
Variable-temperature cryostats developed to study radiation damage to, and annealing of, germanium gamma-ray detectors. Two styles: one accommodates large single detector and one accommodates two medium-sized detectors. New cryostats allow complete testing of large-volume germanium gamma-ray detectors without breaking cryostat vacuum and removing detectors for annealing.
Floyd, Samuel R.↗
Mechanisms delaying glacier retreat in the presence of ocean temperature variability at Thwaites Glacier, Antarctica [Slides]
In this work, we conclude ocean temperature variability affects grounding line evolution and glacier mass loss. As a consequence of local ocean density structure and bathymetry, variable runs always retreat less than steady runs.
54 ENVIRONMENTAL SCIENCES↗
Variable-temperature cryogenic trap for the separation of gas mixtures
The paper describes a continuous variable-temperature U-shaped cold trap which can both purify vacuum-line combustion products for subsequent stable isotopic analysis and isolate the methane and ethane constituents of natural gases. The canister containing the trap is submerged in liquid nitrogen, and, as the gas cools, the gas mixture components condense sequentially according to their relative vapor pressures. After the about 12 min required for the bottom of the trap to reach the liquid-nitrogen temperature, passage of electric current through the resistance wire wrapped around the tubing covering the U-trap permits distillation of successive gas components at optimal temperatures. Data on the separation achieved for two mixtures, the first being typical vacuum-line combustion products of geochemical samples such as rocks and the second being natural gas, are presented, and the thermal behavior and power consumption are reported.
Des Marais, D. J.↗
Temperature variable long path cell for absorption measurements
The design and construction of a long path cell for absorption measurements at temperatures ranging from 215-470 K and at pressures from vacuum to 10 atm are described. The cell consists of three concentric stainless-steel tubes; the innermost tube is 6.5-in. in internal diameter, has a volume of about 47 l, and contains White-type optics, six thermocouples, and a gas input tube; and the outermost tube provides a vacuum Dewar around the inner assembly. The optical design and temperature control system for the long path temperature variable cell are examined. The long path cell is applicable for analyzing temperature and pressure dependence of spectra and reaction rates of gases, and the cell has flow and photolysis capabilities for studying transient species and photochemically initiated reactions. A diagram of the cell is provided.
Shetter, R. E.↗
Impact of the Dominant Large-scale Teleconnections on Winter Temperature Variability over East Asia
Monthly mean geopotential height for the past 33 DJF seasons archived in Modern Era Retrospective analysis for Research and Applications reanalysis is decomposed into the large-scale teleconnection patterns to explain their impacts on winter temperature variability over East Asia. Following Arctic Oscillation (AO) that explains the largest variance, East Atlantic/West Russia (EA/WR), West Pacific (WP) and El Nino-Southern Oscillation (ENSO) are identified as the first four leading modes that significantly explain East Asian winter temperature variation. While the northern part of East Asia north of 50N is prevailed by AO and EA/WR impacts, temperature in the midlatitudes (30N-50N), which include Mongolia, northeastern China, Shandong area, Korea, and Japan, is influenced by combined effect of the four leading teleconnections. ENSO impact on average over 33 winters is relatively weaker than the impact of the other three teleconnections. WP impact, which has received less attention than ENSO in earlier studies, characterizes winter temperatures over Korea, Japan, and central to southern China region south of 30N mainly by advective process from the Pacific. Upper level wave activity fluxes reveal that, for the AO case, the height and circulation anomalies affecting midlatitude East Asian winter temperature is mainly located at higher latitudes north of East Asia. Distribution of the fluxes also explains that the stationary wave train associated with EA/WR propagates southeastward from the western Russia, affecting the East Asian winter temperature. Investigation on the impact of each teleconnection for the selected years reveals that the most dominant teleconnection over East Asia is not the same at all years, indicating a great deal of interannual variability. Comparison in temperature anomaly distributions between observation and temperature anomaly constructed using the combined effect of four leading teleconnections clearly show a reasonable consistency between them, demonstrating that the seasonal winter temperature distributions over East Asia are substantially explained by these four large-scale circulation impacts.
El Nino-Southern Oscillation↗
Infrared-temperature variability in a large agricultural field
Dunnigan Agro-Meteorological Experiment airborne thermal scanner images of a large varying-terrain barley field are acquired and analyzed. Temperature variability that may occur within instantaneous fields of view (IFOV) is defined (coefficient of variation: standard deviation/mean temperature in degrees C), and the percentage of the area within various IFOV's within + or - 1, 2, 3, and 5 degrees of the mean is determined. With the exception of very rugged terrain, over 80% of the area within 4, 16, 65 and 258 ha cells was at temperatures within + or - 3 C of the mean cell temperature. Remote measurements of field temperature appeared to be slightly influenced by pixel size in the range 4 ha to 259 ha, and the area percentage within any pixel which contributes within + or - 1, 2, 3, and 5 degrees C of the mean, is nominally the same. In conclusion, no great advantage is found in utilizing a small IFOV instead of a large one for remote sensing of crop temperature.
Millard, J. P.↗
Subdecadal Holocene Warm-Season Temperature Variability in Central Europe Recorded by Biochemical Varves
Paleoclimate data provide important information about the character of natural climate variability. However, records with sufficient length and resolution to resolve high-frequency (decadal-scale) variability across the Holocene are scarce. We present a 10,800-year reconstruction of spring and summer temperature at three-year resolution based on biochemical varves from Lake $\dot{Z}abi$$\acute{n}skie$, Poland. The reconstruction is based on Ca/Ti ratio, which are significantly correlated with instrumental spring and summer temperature spanning 240 years. Major climate events of the Holocene period are represented in the reconstruction, including the Holocene Thermal Maximum, 8.2 ka Event, Medieval Climate Anomaly, and Little Ice Age. A low-frequency 8,000-year decreasing trend in warm-season temperatures is driven by declining summer insolation. Temperature variability is highest during the early Holocene, likely related to warmer and drier conditions. The rate of warming during the past 90 years is extremely unusual, if not unprecedented for the Holocene, based on our reconstruction.
58 GEOSCIENCES↗
Variable-Temperature Scattering and Spectroscopy Characterizations for Temperature-Dependent Solution Assembly of PffBT4T-Based Conjugated Polymers
The solution structure of conjugated polymers (CPs) from which the films are cast is critical for tailoring the thin-film morphology thus device performance. Here, we used multimodal variable-temperature scattering and spectroscopy tools to fully quantify the solution assembly of poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3'''-dialkyl-2,2';5',2'';5'',2'''-quaterthiophen-5,5'''-diyl)] (PffBT4T) polymers with varying side-chain lengths at different assembly temperatures. The conformational and aggregation behaviors for PffBT4T-based CPs were found to be very sensitive to both temperature and side chain length using ultraviolet–visible (UV–vis) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, dynamic light scattering (DLS), and small-angle neutron scattering (SANS). We found that with slightly increasing side chain length from 2-octyldodecyl (C8C12) to 2-nonyltridecyl (C9C13), PffBT4T-based CPs show a significant decrease in aggregation-to-dissolved chain transition temperature (10 °C), degree of aggregation, enthalpy change of aggregation, and size of the aggregates in solution. At room temperature, PffBT4T polymer strongly aggregated to form fabric structure with the film thickness of a few nanometers in thickness and hundreds of nanometers in length, as probed by atomic force microscopy (AFM), transmission electronic microscopy (TEM), and dynamic light scattering (DLS). At the elevated temperature above the aggregation-to-dissolved chain transition temperature, PffBT4T is fully dissolved and adopts a semiflexible coil conformation with the persistence length of 3.1 nm for PffBT4T-C8C12 and a slightly increased persistence length of 3.4 nm for PffBT4T-C9C13, according to temperature-dependent SANS measurements. Longer side chains of PffBT4T-C9C13 also lead to less aggregation enthalpy gain compared with PffBT4T-C8C12. This work provides a solution structure manipulating strategy of CPs and thus will inspire the molecular design and processing protocols of CPs toward higher performance electronic devices.
36 MATERIALS SCIENCE↗