Thin-Film Differential Scanning Calorimetry:  A New Probe for Assignment of the Glass Transition of Ultrathin Polymer Films

Efremov, Mikhail Yu.; Warren, J. T.; Olson, E. A.; Zhang, M.; Kwan, and A. T.; Allen, L. H.

doi:10.1021/ma0116811

Cited by 64 publications

(60 citation statements)

References 15 publications

(35 reference statements)

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“…For instance, the nanocalorimetry sensor originally developed by Allen and coworkers [15] can attain heating rates as large as 10 5 K/s, but is lower bounded by 10 4 K/s to achieve the adiabatic condition (Eq. (3)) [15].…”

Section: Scanning Calorimetry and Nanocalorimetrymentioning

confidence: 99%

“…(3)) [15]. Schick et al have developed a sensor that can operate under non-adiabatic conditions with controlled heating and cooling rates in the range of 10 3 K/s [16], but its accuracy degrades at lower heating rates.…”

Section: Scanning Calorimetry and Nanocalorimetrymentioning

confidence: 99%

“…Due to the small thermal mass of sensor and sample, very fast heating can be achieved. For instance, the nanocalorimetry sensor originally developed by Allen and coworkers [15] can attain heating rates as large as 10 5 K/s, extending the maximum heating rate of traditional calorimetry by many orders of magnitude. However, the small thermal mass also presents a problem -the measurements are very sensitive to heat loss and the requirement of adiabatic measurement conditions limits the scan rate to this very fast regime.…”

Section: Introductionmentioning

confidence: 99%

“…However, the small thermal mass also presents a problem -the measurements are very sensitive to heat loss and the requirement of adiabatic measurement conditions limits the scan rate to this very fast regime. The fraction of input power that is lost to heat must be small, placing a lower bound on the heating rate, which is 10 4 K/s for the calorimetry sensor developed by Allen and colleagues [15]. Schick et al have developed a sensor that can operate under non-adiabatic conditions with controlled heating and cooling rates in the range of 10 3 K/s [16], but its accuracy degrades at lower heating rates.…”

Section: Introductionmentioning

confidence: 99%

“…This approach has the advantage of being able to measure a large set of similar droplets in a single scan. We perform calorimetry measurements using a nanocalorimeter sensor derived from an original design by Allen and coworkers [3,15], which has negligible thermal lag between sample and temperature sensor thus enabling accurate temperature measurement at very high scanning rates. This nanocalorimeter sensor combined with the appropriate AC-technique [22] is also capable of making accurate measurements at medium to slow scan rates where heat loss to the environment makes DC measurements not practical [81], even allowing in-situ XRD measurements during the scans [26].…”

Section: Introductionmentioning

confidence: 99%

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Scanning AC Nanocalorimetry and Its Applications

Xiao

Vlassak

2016

Fast Scanning Calorimetry

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This thesis presents an AC nanocalorimetry technique that enables calorimetry measurements on very small quantities of materials over a wide range of scanning rates (from isothermal to 3×10^3 K/s), temperatures (up to 1200 K), and environments. Such working range bridges the gap between traditional scanning calorimetry of bulk materials and nanocalorimetry. The method relies on a micromachined nanocalorimeter with negligible thermal lags between heater, thermometer, and sample. The ability to perform calorimetry measurements over such a broad range of scanning rates makes it an ideal tool to characterize the kinetics of phase transformations, reactions at elevated temperatures or to explore the behavior of materials far from equilibrium. We By combining scanning DC and AC nano-calorimetry techniques, we study the nucleation behavior of undercooled liquid Bi at cooling rates ranging from 10^1 to 10^4 K/s. Upon initial melting, the Bi thin-film sample breaks up into isolated islands. The number of islands in a typical sample is sufficiently large that highly repeatable nucleation behavior is observed, despite the stochastic nature of the nucleation process.We establish a data reduction technique to evaluate the nucleation rate from DC and AC calorimetry results. The results show that the driving force for the nucleation of melted Bi is well described by classical nucleation theory over a wide range of cooling rates. The proposed technique provides a unique and efficient way to examine nucleation kinetics v with cooling rates over several orders of magnitude. The technique is quite general and can be used to evaluate reaction kinetics in other materials.Lastly, we apply the scanning AC nanocalorimetry technique to study solid-gas phase reactions by measuring the change in heat capacity of a sample during reaction. We apply this approach to evaluate the oxidation kinetics of thin-film samples of zirconium in air. The results confirm parabolic oxidation kinetics with an activation energy of 0.59±0.03 eV. The nano-calorimetry measurements were performed using a device that contains an array of micromachined nano-calorimeter sensors in an architecture designed for combinatorial studies. We demonstrate that the oxidation kinetics can be quantified using a single sample, thus enabling high-throughput mapping of the composition-dependence of the reaction rate.vi

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Section: Scanning Calorimetry and Nanocalorimetrymentioning

confidence: 99%

Section: Scanning Calorimetry and Nanocalorimetrymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Scanning AC Nanocalorimetry and Its Applications

Xiao

Vlassak

2016

Fast Scanning Calorimetry

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Fast Scanning Calorimetry

Schick

Androsch

2022

Thermal Analysis of Polymeric Materials

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Multiwavelength interferometry and competing optical methods for the thermal probing of thin polymeric films

Vourdas

Karadimos

Goustouridis

et al. 2006

J of Applied Polymer Sci

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Multiple-wavelength interferometry (MWI), a new optical method for the thermal probing of thin polymer films, is introduced and explored. MWI is compared with two standard optical methods, single-wavelength interferometry and spectroscopic ellipsometry, with regard to the detection of the glass transition temperature (T g ) of thin supported polymer films. Poly(methyl methacrylate) films are deposited by spin coating on Si and SiO 2 substrates. MWI is also applied to the study of the effect of film thickness (25-600 nm) and polymer molecular weight (1.5 Â 10 4 to 10 6 ) on T g, the effect of film thickness on the coefficients of thermal expansion both below and above T g , and the effect of deep UV exposure time on the thermal properties (glass transition and degradation temperatures) of the films. This further exploration of the MWI method provides substantial insights about intricate issues pertinent to the thermal behavior of thin polymer films.

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Thin-Film Differential Scanning Calorimetry: A New Probe for Assignment of the Glass Transition of Ultrathin Polymer Films

Cited by 64 publications

References 15 publications

Scanning AC Nanocalorimetry and Its Applications

Scanning AC Nanocalorimetry and Its Applications

Fast Scanning Calorimetry

Multiwavelength interferometry and competing optical methods for the thermal probing of thin polymeric films

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