Temperature Scan Rate Research Articles

Temperature-scan-rate dependent SCO hysteresis found in a tetramethylphosphonium tripodal ferrate(II) salt

A new compound (Me4P)[Fe(py3COH)(NCS)3]•MeOH was prepared and structurally characterized, where py3COH stands for tris(2-pyridyl)methanol. After annealed at 400 K, desolvated (Me4P)[Fe(py3COH)(NCS)3] displayed an abrupt spin-crossover (SCO) at T1/2↑ = 255 K and T1/2↓ = 234 K. Namely, 21 K-wide hysteresis was recorded at a temperature scan rate of 5 K min−1. The χmT vs T profile was temperature-scan rate dependent; the wider hysteresis with the slower scan. The secondary SCO with T1/2↑ = 275 K emerged, and a new concomitant hysteresis loop overlapped the primary one. The total hysteresis width became 39 K at a slow scan with 0.1 K min−1. A mechanism of interplaying spin crossover and structural phase transition is described. Combining a similar result on the corresponding Me4N+ analog, we supposed that the tripod py3COH ligand would have an advantage for hysteretic SCO and possibly for double SCO behavior.

Structural insight into the cooperativity of spin crossover compounds.

Spin-crossover (SCO) compounds are promising materials for a wide variety of industrial applications. However, the fundamental understanding of their nature of transition and its effect on the physical properties are still being fervently explored; the microscopic knowledge of their transition is essential for tailoring their properties. Here an attempt is made to correlate the changes in macroscopic physical properties with microscopic structural changes in the orthorhombic and monoclinic polymorphs of the SCO compound Fe(PM-Bia)2(NCS)2 (PM = N-2'-pyridylmethylene and Bia = 4-aminobiphenyl) by employing single-crystal X-ray diffraction, magnetization and DSC measurements. The dependence of macroscopic properties on cooperativity, highlighting the role of hydrogen bonding, π-π and van der Waals interactions is discussed. Values of entropy, enthalpy and cooperativity are calculated numerically based on the Slichter-Drickamer model. The particle size dependence of the magnetic properties is probed along with the thermal exchange and the kinetic behavior of the two polymorphs based on the dependence of magnetization on temperature scan rate and a theoretical model is proposed for the calculation of the non-equilibrium spin-phase fraction. Also a scan-rate-dependent two-step behavior observed for the orthorhombic polymorph, which is absent for the monoclinic polymorph, is reported. Moreover, it is found that the radiation dose from synchrotron radiation affects the spin-crossover process and shifts the transition region to lower temperatures, implying that the spin crossover can be tuned with radiation damage.

Sub-nL thin-film differential scanning calorimetry chip for rapid thermal analysis of liquid samples.

Differential scanning calorimetry (DSC) is a popular thermal analysis technique. The miniaturization of DSC on chip as thin-film DSC (tfDSC) has been pioneered for the analysis of ultrathin polymer films at temperature scan rates and sensitivities far superior to those attainable with DSC instruments. The adoption of tfDSC chips for the analysis of liquid samples is, however, confronted with various issues including sample evaporation due to the lack of sealed enclosures. Although the subsequent integration of enclosures has been demonstrated in various designs, rarely did those designs exceed the scan rates of DSC instruments mainly because of their bulky features and requirement for exterior heating. Here, we present a tfDSC chip featuring sub-nL thin-film enclosures integrated with resistance temperature detectors (RTDs) and heaters. The chip attains an unprecedented sensitivity of 11 V W-1 and a rapid time constant of 600 ms owing to its low-addenda design and residual heat conduction (∼6 μW K-1). We present results on the phase transition of common liquid crystals which we leverage to calibrate the RTDs and characterize the thermal lag with scan rates up to 900 °C min-1. We then present results on the heat denaturation of lysozyme at various pH values, concentrations, and scan rates. The chip can provide excess heat capacity peaks and enthalpy change steps without much alteration induced by the thermal lag at elevated scan rates up to 100 °C min-1, which is an order of magnitude faster than those of many chip counterparts.

A note on the kinetics of non-isothermal crystallization of polymers

On the kinetics of non-isothermal crystallization of polymers, the reinterpreted Ozawa method proposed in a previous report is studied further to generate valuable information. The Ozawa method is used to investigate the crystallization kinetics with constant temperature scanning rates β and is concerned with the basic formula for apparent crystallinity, from which the true crystallinity is derived using the concept of an extended volume of the Kolmogorov–Johnson–Mehl–Avrami model. The formula is expressed by the temperature scanning rate β and a function of temperature T, βOz(T). This study investigates the temperature derivative of βOz(T), which represents the crystal growth rate in the presence of athermal nucleation from foreign heterogeneities including nucleating agents; this case is applicable to most polymer crystallization processes. The validity of this relationship was verified by comparing it directly to the crystal growth rate in numerical simulations and by comparing it to the crystallization peak and half times of isothermal crystallization for experimental results of poly(butylene terephthalate). This evaluation provides basic information on the crystal growth rate, which is necessary for understanding polymer crystallization. As is well known, the temperature derivative of βOz(T) also corresponds to the function required to derive Nakamura et al. model's suggested equation for polymer processing.

Analyzing effects of temperature gradient and scan rate on metal additive manufacturing microstructure by using phase field-finite element method

Predicting the evolutionary behavior of microstructures with the help of numerical simulation techniques has become an essential tool for studying the solidification process of metal additive manufacturing. As a mesoscopic model based on the diffusion interface theory, phase field method (PFM) can be used to predict the evolution of solidification microstructure. The open-source PFM framework PRISMS-PF can not only efficiently solve systems of equations with billions of degrees of freedom, but also provide a simple adaptive mesh control module. In this paper, based on the open-source PFM framework PRISMS-PF, a phase field-finite element method (PFM-FEM) simulation flow for the solidification process of A356 aluminum alloy additive manufacturing in the two-dimensional case was established. The effects of temperature gradient, scan rate and initial solid-phase morphology on solute concentration, dendrite spacing and dendrite morphology were analyzed and compared with experimental results for verification. Analyzing the results for different temperature gradients and scan rates cases, it was found that the increase of temperature gradient or scan rate made the primary dendrite arm space decrease; as the ratio of temperature gradient to scan rate decreased, the solidification morphology gradually changed from flat crystal to cellular crystal, columnar crystal, and even dendritic structure. Analyzing the results for different initial solid-phase morphology cases, it was found that the influence of initial solid-phase morphology on dendrite growth increased as the ratio of temperature gradient to scan rate decreased. The above influence rules were mainly related to the composition overcooling zone under different conditions. This paper is expected to provide a theoretical support for the effective regulation of solidification microstructure in metal additive manufacturing.

Heat capacity, thermal conductivity and magnetocaloric effect in Heusler alloy Ni-=SUB=-47-=/SUB=-Mn-=SUB=-40-=/SUB=-Sn-=SUB=-13-=/SUB=-

The results of a study of heat capacity, thermal conductivity and magnetocaloric effect of the polycrystalline Ni47Mn40Sn13 alloy depending on temperature (T=80-350 K) and magnetic field (0-8 T) are given. A considerable difference between the values of a sudden change in heat capacity Delta CP in the heating and cooling mode was found near the magnetostructural martensite--austenite phase transition (MSPT), which is related to influence of latent heat of phase transition. Thermal conductivity in the range of T=80-300 K rises with temperature (dkappa/dT>0) and increases in more than three times. Electronic thermal conductivity in the martensitic phase (T=150 K) is 37% of the total value. An anomalous rise of thermal conductivity Deltakappa=kappa(aust)-kappa(mart)=4.2 Wm K was found in the region of MSPT. The contributions of electrons and phonons to the observed sudden change are 63 and 37% respectively and are conditioned both by a rise of mobility of conduction electrons under a martensite--austenite transition and by an increase of phonons' free path length. The magnetocaloric effect in cyclic magnetic fields with the amplitude of 1.8 T was studied. A dependence of reverse effect value on temperature scanning rate was established. The direct measurements of Delta T in the cyclic magnetic field of 1.2 T show a twofold decrease of the effect amplitude near TC at an increase of cyclic magnetic field frequency from 1 to 30 Hz. Most likely, this is related to magnetic and microstructural heterogeneities which act as an additional thermal dissipation channel. Keywords: Heusler alloys, heat capacity, thermal conductivity, magnetocaloric effect, cyclic magnetic fields.

Desolvation–Solvation-Induced Reversible On–Off Switching of Two Memory Channels in a Cobalt(II) Coordination Polymer: Overlay of Spin Crossover and Structural Phase Transition

Desolvation–Solvation-Induced Reversible On–Off Switching of Two Memory Channels in a Cobalt(II) Coordination Polymer: Overlay of Spin Crossover and Structural Phase Transition

Arrhenius behavior of crystallization at up to 184 000 K/s in Ge2Sb2Te5 thin films

We investigate the glass transition and crystallization of Ge2Sb2Te5 by nanocalorimetry on 32–57 nm layers at temperature scanning rates ranging from 23 to 184 kK/s. Crystallization follows the Arrhenius behavior observed at low heating rates, with an activation energy of 2.7 ± 0.1 eV. The crystal-growth velocity (>500 µm/s at 500 K) confirms fast values found in earlier work and by ab initio molecular dynamics simulations. These experiments also outline the importance of carrying out ultra-fast scanning calorimetry studies with samples in excellent thermal contact with the heating device.

Study on nonlinear conduction of PEDOT:PSS conducting polymer

In the present study, solid film of poly (3,4-ethylenedioxythiophene):polystyrenesulfonate, (PEDOT:PSS) has been prepared by casting its aqueous solution at room temperature and are characterized by using X-ray diffraction and differential scanning calorimeter. The temperature-dependent behavior of the ac and dc conductivity of the PEDOT:PSS film has been investigated. The temperature dependence and scan rate dependence of J-V characteristic curves have been tested. The study of frequency dependence of ac conductivity in a wide range of temperature up to 443 K, indicates that the dominant conduction mechanism in PEDOT:PSS film is Overlapping-Large Polaron Tunneling (OLPT). The study of the electrical conduction with applied voltage shows a reversible negative differential resistance (NDR) through the turnover point (T.O.P) for Cu/PEDOT:PSS/Cu device. Threshold current density, Jth, and threshold voltage, Vth at T.O.P as well as NDR are strongly affected by ambient temperature up to 383K and scan rate up to 3V/sec. The turnover behavior has been explained according to a competition between high conduction due to schottky emission and NDR due to field-induced of electrical polarization in conduction paths.

Imaging the Thermal Hysteresis of Single Spin-Crossover Nanoparticles.

The magnetic hysteresis property during the spin transition of spin-crossover (SCO) materials holds great promise for their applications in spin electronics, information storage, thermochromic, and nanophotonic devices. Existing studies often measured the averaged property of a bulk sample consisting of lots of individuals. When considering the significant heterogeneity among different individuals and the inevitable interparticle interactions, ensemble measurement not only blurred the structure-property relationship but also compromised the intrinsic hysteresis property and cyclability. Herein, we employed a recently developed surface plasmon resonance microscopy (SPRM) method to measure the thermal hysteresis curve of single isolated SCO nanoparticles. The thermal-induced spin transition was found to alter the optical contrast of single SCO nanoparticles, which was optically readout using SPRM in a quantitative, nonintrusive, and high-throughput manner. Single nanoparticle measurements revealed an intrinsic transition temperature that was independent of the temperature scan rate and superior stability after over 11 000 cycles of single SCO nanoparticles. Correlations between the hysteresis and the size and morphology of the same individuals further uncovered the significant nanoparticle-to-nanoparticle heterogeneity with implications for the size-property relationship and rational design of SCO materials with improved performance.

On the lipid flip-flop and phase transition coupling.

We measured the passive lipid flip-flop of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) in solid supported lipid bilayers across their main gel to fluid (Lβ → Lα) phase transition. By performing time and temperature resolved neutron reflectometry experiments, we demonstrated that asymmetric systems prepared in the gel phase are stable for at least 24 hours. Lipid flip-flop was found to be intrinsically linked to the amount of lipid molecules in the fluid phase. Moreover, the increase of this amount during the broad phase transition was found to be the main key factor for the timing of the flip-flop process. By measuring different temperature scan rate, we could demonstrate that, in the case of supported bilayers and for the temperature investigated, the lipid flip flop is characterised by an activation energy of 50 kJ mol-1 and a timescale on the order of few hours. Our results demonstrate the origin on the discrepancies between passive flip-flop in bulk systems and at interfaces.

Dependence of pyroelectric response on inter-electrode capacitance for integrated-optical circuits utilizing x-cut LiNbO3 chips

Experimental study of the pyroelectric effect has been made for multi-function integrated-optical circuits (MIOC) utilizing x-cut LiNbO3 chips. It has been experimentally established that pyroelectric voltage is proportional to the temperature scanning rate, and a voltage magnitude depends significantly on capacitances of chip parts between the MIOC electrodes. The pyroelectric effect is considered by us to be an important source of the thermal instability of MIOC. The model of the pyroelectric contribution to the MIOC thermal instability is used to suggest the new methods reducing this instability.

Scale-invariant avalanche dynamics in the temperature-driven martensitic transition of a Cu-Al-Be single crystal

We have combined high sensitivity, extra-low differential temperature scanning rate calorimetry, and acoustic emission (AE) measurements to study avalanches during the cubic \ensuremath{\leftrightarrow} 18R martensitic transition of a Cu-Al-Be single crystalline shape memory alloy. Both AE and calorimetry corroborate a good power-law behavior for cooling with an exponent $\ensuremath{\varepsilon}\ensuremath{\simeq}1.6$. For heating, a slope is observed in the maximum likelihood curves, which confirms that our data are affected by an exponential cutoff. An effective energy exponent, $\ensuremath{\varepsilon}\ensuremath{\sim}1.85$, and a cutoff, ${\ensuremath{\lambda}}^{\ensuremath{-}1}=0.115(38)\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}3}\phantom{\rule{0.16em}{0ex}}\mathrm{aJ}$, were determined by fits of power-laws with exponential damping. The long tail observed in the low-temperature region by calorimetric measurements suggests the existence of significant elastic effects that constrain the progress of the transformation at low temperatures. While thermodynamic features such as transformation enthalpy and entropy are those expected for Cu-based shape-memory alloys undergoing a cubic \ensuremath{\leftrightarrow} 18R transition, the critical behavior deviates from the corresponding behavior expected from this symmetry change. These deviations are a consequence of the elastic hardening induced by the interplay of the transformation with dislocation jamming, which has the effect of effectively reducing the number of pathways connecting the parent and martensitic phase.

Study of triplet kinetic of thermal decomposition reaction and sensitivity to impact and electrostatic discharge of HMX polymorphs

The polymorphs of HMX explosive show the different sensitivities to heat, friction, impact, shock, electrostatic charge, etc. Knowledge and understanding of the relationship between polymorphism and these parameters in crystalline HMX phases may enable improvement in existing energetic compounds or development of novel materials. The kinetic behavior of thermal decomposition of α-HMX, β-HMX and γ-HMX was studied by non-isothermal TG/DSC technique at different temperature scan rates. Using KAS isoconversional method, the mean activation energies of 402.81, 389.93 and 364.85 kJ mol−1 were obtained for β-HMX, α-HMX and γ-HMX, respectively, showing the higher thermal stability of β-HMX than γ-HMX and α-HMX. Moreover, the model of thermal decomposition reaction of studied samples was found in Avrami–Erofeev A3/2 with differential function of 3/2(1 − α)[− Ln (1 − α)]1/3. The results of sensitivity to impact and electrostatic discharge (ESD) were also shown the β-HMX is more sensitive to ESD test than γ-HMX and α-HMX. The morphology of the HMX polymorphs was also discussed by the images of the scanning electron microscope.

Discrimination between two memory channels by molecular alloying in a doubly bistable spin crossover material.

A multistable spin crossover (SCO) molecular alloy system [Fe1-x M x (nBu-im)3(tren)](P1-y As y F6)2 (M = ZnII, NiII; (nBu-im)3(tren) = tris(n-butyl-imidazol(2-ethylamino))amine) has been synthesized and characterized. By controlling the composition of this isomorphous series, two cooperative thermally induced SCO events featuring distinct critical temperatures (T c) and hysteresis widths (ΔT c, memory) can be selected at will. The pristine derivative 100As (x = 0, y = 1) displays a strong cooperative two-step SCO and two reversible structural phase transitions (PTs). The low temperature PTLT and the SCO occur synchronously involving conformational changes of the ligand's n-butyl arms and two different arrangements of the AsF6 - anions [T1c = 174 K (ΔT1c = 17 K), T2c = 191 K (ΔT2c = 23 K) (scan rate 2 K min-1)]. The high-temperature PTHT takes place in the high-spin state domain and essentially involves rearrangement of the AsF6 - anions [TPTc = 275 K (ΔTPTc = 16 K)]. This behavior strongly contrasts with that of the homologous 100P [x = 0, y = 0] derivative where two separate cooperative one-step SCO can be selected by controlling the kinetics of the coupled PTLT at ambient pressure: (i) one at low temperatures, T c = 122 K (ΔT c = 9 K), for temperature scan rates (>1 K min-1) (memory channel A) where the structural modifications associated with PTLS are inhibited; (ii) the other centered at T c = 155 K (ΔT c = 41 K) for slower temperature scan rates ≤0.1 K min-1 (memory channel B). These two SCO regimes of the 100P derivative transform reversibly into the two-step SCO of 100As upon application of hydrostatic pressure (ca. 0.1 GPa) denoting the subtle effect of internal chemical pressure on the SCO behavior. Precise control of AsF6 - ↔ PF6 - substitution, and hence of the PTLT kinetics, selectively selects the memory channel B of 100P when x = 0 and y ≈ 0.7. Meanwhile, substitution of FeII with ZnII or NiII [x ≈ 0.2, y = 0] favors the low temperature memory channel A at any scan rate. This intriguing interplay between PT, SCO and isomorphous substitution was monitored by single crystal and powder X-ray diffractometries, and magnetic and calorimetric measurements.

One-Dimensional Thiocyanato-Bridged Fe(II) Spin Crossover Cooperative Polymer With Unusual FeN5S Coordination Sphere.

We present here a novel example of spin crossover phenomenon on a Fe(II) one-dimensional chain with unusual N5S coordination sphere. The [{Fe(tpc-OMe)(NCS)(μ-NCS)} n] (1) compound was prepared using the tridentate tpc-OMe ligand (tpc-OMe = tris(2-pyridyl)methoxymethane), FeCl2·4H2O, and the KSCN salt. Crystallographic investigations revealed that the Fe(II) ions are connected by a single bridging NCS- ligand (μ-κN:κS-SCN coordination mode) to afford a zigzag neutral chain running along the [010] direction, in which the thiocyanato bridging groups adopt a cis head-to-tail configuration. The (N5S) metal environment arises from one thiocyanato-κS and two thiocyanato-κN ligands and from three pyridine of the fac-tpc-OMe tripodal ligand. This compound presents a unique extension of Fe(II) binuclear complexes into linear chains built on similar tripodal ligands and bridging thiocyanate anions. Compound 1 shows a spin crossover (SCO) behavior which has been evidenced by magnetic, calorimetric, and structural investigations, revealing a sharp cooperative spin transition with a transition temperature of ca. 199 K. Temperature scan rate studies revealed a very narrow hysteresis loop (∼1 K wide). Photoswitching of this compound was also performed, evidencing a very fast relaxation process at low temperature. Among other factors, the linearity of the N-bound terminal thiocyanato ligand appears as the main structural characteristic at the origin of the presence of the SCO transition in compound 1 and in the two others Fe(II) previous systems involving thiocyanato-bridges and tripodal tris(2-pyridyl)methane ligands.

Kinetic Spinodal Instabilities in the Mott Transition in V_{2}O_{3}: Evidence from Hysteresis Scaling and Dissipative Phase Ordering.

We present the first systematic observation of scaling of thermal hysteresis with the temperature scanning rate around an abrupt thermodynamic transition in correlated electron systems. We show that the depth of supercooling and superheating in vanadium sesquioxide (V_{2}O_{3}) shifts with the temperature quench rates. The dynamic scaling exponent is close to the mean field prediction of 2/3. These observations, combined with the purely dissipative continuous ordering seen in "quench-and-hold" experiments, indicate departures from classical nucleation theory toward a barrier-free phase ordering associated with critical dynamics. Observation of critical-like features and scaling in a thermally induced abrupt phase transition suggests that the presence of a spinodal-like instability is not just an artifact of the mean field theories but can also exist in the transformation kinetics of real systems, surviving fluctuations.

Fast scanning calorimetry of lysozyme unfolding at scanning rates from 5 K/min to 500,000 K/min

BackgroundProtein denaturation is often studied using differential scanning calorimetry (DSC). However, conventional instruments are limited in the temperature scanning rate available. Fast scanning calorimetry (FSC) provides an ability to study processes at much higher rates while using extremely small sample masses [ng]. This makes it a very interesting technique for protein investigation. MethodsA combination of conventional DSC and fast scanning calorimeters was used to study denaturation of lysozyme dissolved in glycerol. Glycerol was chosen as a solvent to prevent evaporation from the micro-sized samples of the fast scanning calorimeter. ResultsThe lysozyme denaturation temperatures in the range of scanning rates from 5 K/min to ca. 500,000 K/min follow the Arrhenius law. The experimental results for FSC and conventional DSC fall into two distinct clusters in a Kissinger plot, which are well approximated by two parallel straight lines. ConclusionsThe transition temperatures for the unfolding process measured on fast scanning calorimetry sensor are significantly lower than what could be expected from the results of conventional DSC using extrapolation to high scanning rates. Evidence for the influence of the relative surface area on the unfolding temperature was found. General significanceFor the first time, fast scanning calorimetry was employed to study protein denaturation with a range of temperature scanning rates of 5 orders of magnitude. Decreased thermal stability of the micro-sized samples on the fast scanning calorimeter raise caution over using bulk solution thermal stability data of proteins for applications where micro-sized dispersed protein solutions are used, e.g., spray drying.

Novel voltage signal at proximity-induced superconducting transition temperature in gold nanowires

We observed a novel voltage peak in the proximity effect induced superconducting gold (Au) nanowire while cooling the sample through the superconducting transition temperature. The voltage peak turned into dip in the warming process. The voltage peak (or dip) was found to be closely related to the emergence (vanishing) of the proximity induced superconductivity in the Au nanowire. The amplitude of the voltage signal depends on the temperature scanning rate and it cannot be detected when the temperature is changed slower than 0.03 K/min. This transient feature suggests the non-equilibrium property of the effect. The voltage peak could be understood by Ginzburg-Landau model as a combined result of the emergence of Cooper pairs with relatively lower free energy in W contact and the non-equilibrium diffusion of Cooper pairs and quasiparticles.

An investigation of operating conditions on anodic oxidation of synthetic sulfide-containing wastewaters at the surface of a platinum electrode using cyclic voltammetry

In this paper, cyclic voltammetry (CV) was used to study the effects of operating parameters (i.e., sulfide concentration, sodium chloride concentration as supporting electrolyte, temperature, mixing speed, and potential scan rate) on the anodic oxidation of synthetic sulfide-containing wastewaters at the surface of a platinum electrode. The results revealed that anodic oxidation could be used to eliminate sulfide from wastewaters in a wide concentration range, and the oxidation current was an ascending function of the sulfide concentration. The supporting electrolyte concentration had a negligible effect, as the sulfide dissociated in the aqueous media and brought electrical conductivity to the solution. The optimum concentration of electrolyte was found to be 0.05 mol/L. Increasing temperature improved the kinetics of the oxidation reactions and enhanced the electrical conductivity of the solution, which resulted in increasing the anodic oxidation rate. However, at higher temperatures, undesired side reactions were activated which resulted in lowering the power efficiency of the desired anodic oxidation reactions. The optimum operating temperature was found to be 40 – 60 °C. The mixing speed had a periodic effect on the sulfide oxidation. It decreased the diffusion resistance and also the residence time of sulfide at the electrode surface. These phenomena affected the anodic oxidation oppositely and hence, a middle value around 200 rpm was found to be the optimum. By increasing the potential scan rate, the time of performing the reactions in each cycle increased and the overall oxidation progress improved. It was found that mass transfer resistance was a limiting step in the overall reaction. Based on the findings, anodic oxidation has the potential for treating sulfide-containing wastewaters and in the future may be a competitor for conventional treatment processes.