Yeong Zen Chua

High frequency alternating current chip nano calorimeter with laser heating

Heat capacity spectroscopy at frequencies up to 100 kHz is commonly performed by thermal effusivity measurements applying the 3ω-technique. Here we show that AC-calorimetry using a thin film chip sensor allows for the measurement of frequency dependent heat capacity in the thin film limit up to about 1 MHz. Using films thinner than the thermal length of the thermal wave (~1 μm) at such frequencies is advantageous because it provides heat capacity alone and not in combination with other quantities like thermal conductivity, at least on a qualitative basis. The used calorimetric sensor and the sample are each less than 1 μm thick. For high frequency AC-calorimetry, high cooling rates at very small temperature differences are required. This is realized by minimizing the heated spot to the size of the on chip thermocouple (3 × 6 μm(2)). A modulated laser beam shaped and positioned by a glass fiber is used as the heat source. The device was used to measure the complex heat capacity in the vicinity of the dynamic glass transition (structural relaxation) of poly(methyl methacrylate). Combining different calorimeters finally provides data between 10(-3) Hz and 10(6) Hz. In this frequency range the dynamic glass transition shifts about 120 K.

Temperature fluctuations and the thermodynamic determination of the cooperativity length in glass forming liquids

The aim of this paper is to decide which of the two possible thermodynamic expressions for the cooperativity length in glass forming liquids is the correct one. In the derivation of these two expressions, the occurrence of temperature fluctuations in the considered nanoscale subsystems is either included or neglected. Consequently, our analysis gives also an answer to the widely discussed problem whether temperature fluctuations have to be generally accounted for in thermodynamics or not. To this end, the characteristic length-scales at equal times and temperatures for propylene glycol were determined independently from AC calorimetry in both the above specified ways and from quasielastic neutron scattering (QENS), and compared. The result shows that the cooperative length determined from QENS coincides most consistently with the cooperativity length determined from AC calorimetry measurements for the case that the effect of temperature fluctuations is incorporated in the description. This conclusion indicates that-accounting for temperature fluctuations-the characteristic length can be derived by thermodynamic considerations from the specific parameters of the liquid at glass transition and that temperature does fluctuate in small systems.

Dynamics of supercooled liquid and plastic crystalline ethanol: Dielectric relaxation and AC nanocalorimetry distinguish structural α- and Debye relaxation processes

Physical vapor deposition has been used to prepare glasses of ethanol. Upon heating, the glasses transformed into the supercooled liquid phase and then crystallized into the plastic crystal phase. The dynamic glass transition of the supercooled liquid is successfully measured by AC nanocalorimetry, and preliminary results for the plastic crystal are obtained. The frequency dependences of these dynamic glass transitions observed by AC nanocalorimetry are in disagreement with conclusions from previously published dielectric spectra of ethanol. Existing dielectric loss spectra have been carefully re-evaluated considering a Debye peak, which is a typical feature in the dielectric loss spectra of monohydroxy alcohols. The re-evaluated dielectric fits reveal a prominent dielectric Debye peak, a smaller and asymmetrically broadened peak, which is identified as the signature of the structural α-relaxation and a Johari-Goldstein secondary relaxation process. This new assignment of the dielectric processes is supported by the observation that the AC nanocalorimetry dynamic glass transition temperature, Tα, coincides with the dielectric structural α-relaxation process rather than the Debye process. The combined results from dielectric spectroscopy and AC nanocalorimetry on the plastic crystal of ethanol suggest the occurrence of a Debye process also in the plastic crystal phase.

New experimental melting properties as access for predicting amino-acid solubility

The properties of melting are required for the prediction of solubility of solid compounds. Unfortunately, direct determination of the enthalpy of fusion and melting temperature by using conventional DSC or adiabatic calorimetry is often not possible for biological compounds due to decomposition during the measurement. To overcome this, fast scanning calorimetry (FSC) with scanning rates up to 2 × 104 K s−1 was used in this work to measure the melting parameters for L-alanine and glycine. The enthalpy of fusion and melting temperature (extrapolated to zero heating rate) were ΔfusH = (22 ± 5) kJ mol−1 and Tfus = (608 ± 9) K for L-alanine, and ΔfusH = (21 ± 4) kJ mol−1 and Tfus = (569 ± 7) K for glycine. These melting properties were used in the modeling framework PC-SAFT to predict amino-acid solubility in water. The pure-component PC-SAFT parameters and one binary parameter were taken from literature, in which these parameters were fitted to solubility-independent thermodynamic properties such as osmotic coefficients or mixture densities. It was shown that this allowed accurately predicting amino-acid solubility in water over a broad temperature range. The combined methodology of PC-SAFT and FSC proposed in this work opens the door for predicting solubility of molecules that decompose before melting.

First Clear-Cut Experimental Evidence of a Glass Transition in a Polymer with Intrinsic Microporosity: PIM-1

Polymers with intrinsic microporosity (PIMs) represent a novel, innovative class of materials with great potential in various applications from high-performance gas-separation membranes to electronic devices. Here, for the first time, for PIM-1, as the archetypal PIM, fast scanning calorimetry provides definitive evidence of a glass transition ( Tg = 715 K, heating rate 3 × 104 K/s) by decoupling the time scales responsible for glass transition and decomposition. Because the rigid molecular structure of PIM-1 prevents any conformational changes, small-scale bend and flex fluctuations must be considered the origin of its glass transition. This result has strong implications for the fundamental understanding of the glass transition and for the physical aging of PIMs and other complex polymers, both topical problems of materials science.