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This is the final report of CMS FAST OPTICAL CALORIMETRY, a grant to Fairfield University for development, construction, installation and operation of the forward calorimeter on CMS, and for upgrades of the forward and endcap calorimeters for higher luminosity and radiation damage amelioration.
Recently at Los Alamos National Laboratory, sophisticated prediction algorithms have been considered for the use of calorimetry for treaty verification. These algorithms aim to predict the equilibrium temperature based on early data and therefore be able to shorten the measurement time while maintaining good accuracy. The algorithms have been implemented in MATLAB and applied on existing equilibrium measurements from a spent nuclear fuel calorimeter located at the Swedish nuclear fuel interim storage facility. The results show significant improvements in measurement time in the order of 15 to 50 compared to equilibrium measurements, but cannot predict the heat accurately in less time than the currently used temperature increase method can. This Is both due to uncertainties in the calibration of the method as well as identified design features of the calorimeter that limits the usefulness of equilibrium type measurements. The conclusions of these findings are discussed, and suggestions of both improvements of the current calorimeter as well as what to keep in mind in a new design are given.
Animal and human calorimetry, human responses to cold skin and to high cortical temperature, human thermoregulator
Crystallinity index measurements of poly/ethylene terephthalate/ by X-ray diffractometric and differential scanning calorimetry index methods
To guide development of microwave process technology that could be used during in situ construction on the Moon, we measured the high-temperature basic dielectric properties (εʹ and εʺ) of 17 lunar simulants and related materials. In order to confidently use these data one needs to understand the data’s strengths and weaknesses. Therefore, a goal of this publication is to provide insights into the comparative effects of sample composition, pre-treatments, experimental variables, high temperatures, and other factors on the measured response. The dielectric measurements were performed using the cavity perturbation method over a temperature range between room temperature to 1000 °C, or higher, and provided the real and imaginary components of permittivity at six frequencies. The utility of the original values was limited by the varying density of the pellets used in the measurement. Therefore, all of the εʹ and εʺ measurements at the frequency of 2466 MHz have been scaled to a constant density, 1.75 g/cm 3 . Here the data are presented as graphs chosen to aid analysis within and across simulant groups. To gain additional insight into the processes happening at the elevated temperatures in the dielectric measurements, heat capacity data was obtained using differential scanning calorimetry (DSC) on several of the simulant materials. Our data show that over the frequency range 397 MHz – 2985 MHz a material’s behavior does not greatly change, as compared to the scale of differences observed between lunar mare and highland simulants at high temperatures. For example at 1000 °C, the mare simulant JSC-1A absorbs 10 times more power than the highland simulant NUW-LHT-5M. We observe that as melting temperatures are reached both permittivity and dielectric loss rise non-linearly, helping to explain thermal runaway during microware heating. Our data show that even less than a few weight % of many non-lunar minerals, and the use of mixtures in simulants can affect the dielectric behavior at higher temperatures. A comparison of our results with published dielectric data for Apollo samples and with remote sensing of the Moon supports the conclusion the simulants and lunar material at room temperature have very similar dielectric values.
Because of its extremely high thermal conductivity, measuring the thermal conductivity or diffusivity of optical-grade diamond can be challenging. Various methods have been used to measure the thermal conductivity of thick diamond films. For the purposes of commercial quality control, the AC laser calorimetry method is appealing because it enables fairly rapid and convenient sample preparation and measurement. In this paper, the method is used to measure the thermal diffusivity of optical diamond. It is found that sample dimensions and measurement parameters are critical, and data analysis must be performed with great care. The results suggest that the method as it is applied to optical-grade diamond could be enhanced by a more powerful laser, higher frequency beam modulation, and post-processing based on 2D thermal simulation.
Thermomechanical properties of polymers greatly depend on their glass transition temperature ( T g ). Differential scanning calorimetry (DSC) is commonly used to measure T g of polymers. Yet, many conjugated polymers (CPs), especially donor–acceptor CPs (D–A CPs), do not show a clear glass transition when measured by conventional DSC using simple heat and cool scan. In this work, we discuss the origin of the difficulty for measuring T g in such type of polymers. The changes in specific heat capacity (Δ c p ) at T g were accurately probed for a series of CPs by DSC. The results showed a significant decrease in Δ c p from flexible polymer (0.28 Jg -1 K -1 for polystyrene) to rigid CPs (10 -3 Jg -1 K -1 for a naphthalene diimide-based D–A CP). When a conjugation breaker unit (flexible unit) is added to the D–A CPs, we observed restoration of the Δ c p at T g by a factor of 10, confirming that backbone rigidity reduces the Δ c p . Additionally, an increase in the crystalline fraction of the CPs further reduces Δ c p . We conclude that the difficulties of determining T g for CPs using DSC are mainly due to rigid backbone and semicrystalline nature. We also demonstrate that physical aging can be used on DSC to help locate and confirm the glass transition for D-A CPs with weak transition signals.
Linear starch form inclusion complexes with fatty acids through hydrophobic interaction. The complexation between starch and fatty acid is affected by many factors, such as starch degree of polymerization (DP), fatty acid structure, and complexation conditions. There is limited information on the use of isothermal titration calorimetry (ITC) in understanding starch‐fatty acid interactions. The effects of temperature and concentration of hexanoic acid on the complexation of debranched waxy maize starch and potato amylose were investigated using ITC. The starch samples were characterized for their molecular size distribution and iodine affinity. Potato amylose and debranched waxy maize starch displayed a major peak DP of 330 and 25, and iodine affinity of 2.9 and 13.9, respectively. The ITC titration data were fitted best to a one set of binding site model. Complexation was exothermic and spontaneous for all reactions based on changes in enthalpy of free energy (ΔG). The binding affinity ( K a ) of debranched waxy maize starch for hexanoic acid decreased with an increase in temperature from 25 to 45°C. The K a and number of binding sites ( n ) for debranched waxy maize exceeded those of potato amylose, indicating a higher complexation of debranched waxy maize for hexanoic acid. The number of binding sites ( n ) and enthalpy of binding (Δ H ) values for both starches remained independent of temperature change. The ITC results demonstrated that debranched waxy maize starch was favored over potato amylose to complex hexanoic acid.
In this study, a suite of experimental tools and fast-acting, numerical-simulation techniques was used to quantify the precipitation behavior of three nickel-base superalloys: IN-100, LSHR, and 718. Experimental methods comprised differential scanning calorimetry (DSC) to establish the specific heat as a function of temperature and selected direct-resistance heating trials (using a Gleeble ® machine) to obtain samples for microstructural analysis. For the DSC experiments, each alloy was cooled at a prescribed constant rate (between 5 and 20 K/min) after an initial soak/equilibration in the high-temperature, single-phase (supersolvus) temperature regime. On-heating DSC trials beginning at ambient temperature were also performed on alloy 718 in three different starting conditions: super- δ -solvus solution treated and water quenched (denoted as ST), solution treated and aged (STA), and solution treated and overaged (STOA). DSC results, revealing the thermal signatures associated with the kinetics of precipitation of γ ' (IN-100, LSHR) or γ ' and γ " (718), were interpreted using a previously-developed fast-acting routine that treats concurrent nucleation, growth, coarsening, and dissolution. For these simulations, special attention was paid to various thermo-kinetic input parameters including equilibrium solvus-approach curves, bulk free energies of transformation, matrix-precipitate interface energies, and effective diffusivities. For the γ - γ ' superalloys (IN-100 and LSHR), estimates of precipitate volume fraction as a function of temperature from the specific-heat data revealed semi-quantitative agreement with simulation predictions. For the γ - γ '- γ " superalloy (718), simulation predictions of precipitate volume fractions were converted to specific heat as a function of temperature and showed semi-quantitative agreement with the direct measurements.
Using fast scanning calorimetry (FSC), we investigated the glass transition and crystal melting of samples of B. mori silk fibroin containing Silk I and/or Silk II crystals. Due to the very short residence times at high temperatures during such measurements, thermal decomposition of silk protein can be significantly suppressed. FSC was performed at 2000 K/s using the Mettler Flash DSC1 on fibroin films with masses around 130–270 ng. Films were prepared with different crystalline fractions (ranging from 0.26 to 0.50) and with different crystal structures (Silk I, Silk II, or mixed) by varying the processing conditions. These included water annealing at different temperatures, exposure to 50% MeOH in water, or autoclaving. The resulting crystal structure was examined using wide angle X-ray scattering. Degree of crystallinity was evaluated from Fourier transform infrared (FTIR) spectroscopy and from analysis of the heat capacity increment at the glass transition temperature. Silk fibroin films prepared by water annealing at 25 °C were the least crystalline and had Silk I structure. FTIR and FSC studies showed that films prepared by autoclaving or 50% MeOH exposure were the most crystalline and had Silk II structure. Intermediate crystalline fraction and mixed Silk I/Silk II structures were found in films prepared by water annealing at 37 °C. FSC results indicate that Silk II crystals exhibit endotherms of narrower width and have higher mean melting temperature Tm(II) = 351 ± 2.6 °C, compared to Silk I crystals which melt at Tm(I) = 292 ± 3.8 °C. Films containing mixed Silk I/Silk II structure showed two clearly separated endothermic peaks. Evidence suggests that the two types of crystals melt separately and do not thermally interconvert on the extremely short time scale (0.065 s between onset and end of melting) of the FSC experiment.
Here, phase formation in the mixed sulfate–selenate Np(VI)-bearing aqueous system has been investigated. The obtained crystalline compounds, Cs 2 [(NpO 2 ) 2 (TO 4 ) 3 ] (T = S, Se), crystallize in the tetragonal system, space group P$\bar{42}$ 1 m, with a = 9.5737(3)–9.817(3) Å, c = 8.0824(4)–8.111(3) Å, and V = 740.79(6)–781.8(6) Å 3 , and have been chemically characterized. Single-crystal X-ray diffraction experiments at various temperatures were used to define the thermal behavior of the crystal structures relative to the S/Se ratio. The thermal behavior of mixed sulfate–selenate and pure selenate compounds is anisotropic, with the highest thermal expansion in the direction perpendicular to the sheets of Np-bearing polyhedra, while the structure of the pure sulfate compound experiences almost isotropic thermal expansion with slightly higher expansion within the layer, which is explained by the influence of stronger Cs–O bonding. High-temperature drop solution calorimetry was used to derive the enthalpies of formation of the Cs + -bearing neptunyl oxysalts. Lastly, within this family of isotypic structures, cesium neptunyl sulfate has a more negative enthalpy of formation in comparison to the selenate compound.
We report the use of aqueous phase separations via aqueous biphasic systems (ABS) has been widely explored in the recent decades. For wider and more “intelligent” applications, it is important to look below the surface and study these systems thoroughly at a fundamental level. Two important questions still unsolved are how do polymers and ions of different types organize water (if they in fact they do so) and how does it affect the separation of phases? In the present work, differential scanning calorimetry (DSC) was used to relate ABS phase diagrams and the behavior of water in aqueous solutions containing kosmotropic salts (K 3 PO 4 or (NH 4 ) 2 SO 4 ), a chaotropic ionic liquid ([C 4 mim]Cl), or a polymer (PEG-2000), all of which are reported components of ABS, and their mixtures. Additional DSC transitions were observed for the two classes of salts which could be assigned based on the fundamental differences between their interactions with water, suggesting that it is the differences in the abilities of kosmotropic and chaotropic salts to interact with water which result in the phase separation phenomena observed. The DSC measurements of solutions of PEG-2000 and (NH 4 ) 2 SO 4 indicate that aqueous solutions of PEG-2000 supercool and potentially enter a glassy state that exhibits devitrification upon heating. The devitrified state exhibits a clear eutectic with water. Mixtures of the polymer and salt continue to exhibit all the features observed for the pure components. These results suggest that the mixtures are phase separated and consist of largely separate concentrated solutions of PEG-2000 and (NH 4 ) 2 SO 4 , indicating an entropy-driven phase separation. The DSC analysis of these systems further refines the understanding of kosmotropic and chaotropic solutes into more specific phenomena for each compound. Lastly, this work suggests that DSC can be used to understand the role of each salt/component in ABS.
The heat of adsorption of Cu vapor versus coverage was measured on rutile-TiO 2 (100) at 300 and 100 K using single-crystal adsorption calorimetry. At these conditions, Cu nanoparticles nucleate and then grow larger. The average Cu particle size versus Cu coverage was measured using He + low-energy ion scattering spectroscopy. These data were analyzed with the recently introduced spherical cap model (SCM) to provide the heat of Cu adsorption and Cu chemical potential versus Cu particle size, as well as the contact angle (67°) and adhesion energy (2.50 J/m 2 ) at the Cu particle/rutile-TiO 2 (100) interface. The hemispherical cap model (HCM) was used to model the data first, and then those HCM results were converted to the more accurate SCM results using a recently published mathematical approximation whose high accuracy was validated here. Furthermore, the adhesion energy of Cu on rutile-TiO 2 (100) measured here is compared to prior values for Ag and Au on rutile-TiO 2 (100), showing a nearly proportional increase in adhesion energy with metal oxophilicity (per unit area).
Despite the importance of noncovalent interactions in the utilization of metal–organic frameworks (MOFs), using these interactions to functionalize MOFs has rarely been explored. The ease of functionalization and potential for surface-selective functionalization makes modification via noncovalent interactions promising for the creation of porous photocatalytic assemblies. Here, using isothermal titration calorimetry, photoluminescence measurements, and desorption experiments, we have explored the nature and magnitude of the interactions of [Ru(bpy) 2 (bpy-R)] 2+ -functionalized dyes with the surface of MIL-96, where R = C 3 , C 8 , C 12 , and C 18 alkyl chains of either straight-chain or cyclic conformations. The orientation of the dyes appears to be flat against the surface with respect to the long alkyl chains, and the surface concentration approaches a monolayer at high initial concentrations of dye. Strangely, the dodecyl-functionalized dye, despite having a smaller interaction energy and larger footprint than either octyl-functionalized dye, achieves the highest maximum surface concentration. Based on photoluminescence spectra, desorption experiments, and ITC data, we believe this is due to the core of the dye being lifted from the surface as the chain length increases. Our understanding of these interactions is important for further utilization of this method for the functionalization of the internal and external surface areas of MOFs.
Interest in the use of carbon supports for late transition metal nanoparticle catalysts has expanded rapidly due to the increasing importance of electrocatalysts for clean energy and environmental technologies and the use and storage of renewable electricity. Compared to oxide supports, almost nothing is known about the effect of metal nanoparticle size on the energies of the metal atoms within carbon-supported nanoparticles, yet these energies are crucial for understanding their surface reactivity and sintering kinetics. Here, the growth morphology and adsorption energetics of vapor-deposited Ag onto clean graphene/Ni(111) surfaces have been studied using a combination of single-crystal adsorption calorimetry (SCAC) and He + low-energy ion scattering (LEIS). The differential heat of Ag adsorption is 207 kJ/mol for making ~30 atom Ag particles on graphene terraces at 100 K and 16 kJ/mol higher for making ~9 atom Ag clusters at defect sites at the same temperature. The heat of adsorption increases rapidly with Ag coverage as 3D Ag nanoparticles nucleate and grow in size, asymptotically reaching within 5 kJ/mol of the bulk Ag sublimation enthalpy (285 kJ/mol) by 2 ML. The heats of adsorption and Ag nanoparticle densities from LEIS (~10 16 /m 2 ) were combined to provide the Ag/graphene adhesion energy (E adh = 1.8 J/m 2 in the large-particle limit) and the Ag chemical potential (μ) versus effective particle diameter (D). The Ag chemical potential was well-fitted by μ(D) = (3γ v /M – E adh )(1 + (1.5 nm)/D)(2V m /D), where γ v /M is the surface energy of bulk Ag and V m is its molar volume. The same equation is known to fit similar data for late transition metals on clean surfaces of metal oxide single crystals. The adhesion energy of Ag measured here on graphene falls within the wide range measured for Ag on those oxide surfaces and is almost as large as on the oxide that binds Ag particles most strongly, namely CeO 2 (111), which is well-known to be very effective at resisting catalyst deactivation by metal sintering. Furthermore, these results imply that carbon supports will be effective at resisting sintering and that Ag particles smaller than 6 nm on graphene will bind small adsorbed reaction intermediates more weakly than supports with weaker adhesion to Ag, like MgO(100).
Room temperature calorimetry methods were developed to describe the energy landscapes of six polyoxometalates (POMs), Li–U 24 , Li–U 28 , K–U 28 , Li/K–U 60 , Mo 132 , and Mo 154 , in terms of three components: enthalpy of dissolution (ΔH diss ), enthalpy of formation of aqueous POMs (ΔH f,(aq) ), and enthalpy of formation of POM crystals (ΔH f,(c) ). ΔH diss is controlled by a combination of cation solvation enthalpy and the favorability of cation interactions with binding sites on the POM. In the case of the four uranyl peroxide POMs studied, clusters with hydroxide bridges have lower ΔH f,(aq) and are more stable than those containing only peroxide bridges. Here, in general for POMs, the combination of calorimetric results and synthetic observations suggest that spherical topologies may be more stable than wheel-like clusters, and ΔH f,(aq) can be accurately estimated using only ΔH f,(c) values owing to the dominance of the clusters in determining the energetics of POM crystals.
Chemotherapy is a primary treatment for the metastatic lung cancer patients. To select the most effective combination of drugs, we need an efficient way of assessing tumor response. Here, we showed that differential scanning calorimetry (DSC) analysis of blood serum proteins could reveal the patient response to the treatment. If chemotherapy is effective, serum proteins DSC curve of non-small cellular lung cancer (NSCLC) case is similar to the those of the healthy individuals. If treatment fails, notable changes occur in the DSC profile of NSCLC patient’s blood serum. Our preliminary work illustrates how thermal analysis of changes in the heat capacity of blood serum proteins can provide an insight into patient response to chemotherapy – the essential information for any successive lung cancer treatment.
Dual-readout and particle flow algorithm (PFA) are technologies proposed for precise jet energy measurement in future colliders. While PFA requires highly granular calorimeters, dual-readout has mainly been used with fiber-based calorimeters that do not have highly segmented capabilities. It is still non-trivial to combine these two technologies in one calorimeter system because of the use of fibers in most of the dualreadout calorimeters, which is not compatible with the high granularity requirement of PFA technologies. The aim of this study is to develop a novel calorimetry that combines dual-readout and PFA by adopting a highly segmented tile-based configuration. This paper compares the improvement of energy resolution using dual-readout approach across several configurations of highly granular hadron calorimeters through simulation. Results indicate that setups with fine sampling and close placement of scintillators and Cherenkov detectors improve dual-readout performance.