Feng Yi, National Institute of Standards and Technology
Leslie Allen, University of Illinois at Urbana
Martin Kuball, University of Bristol
Sindee Simon, Texas Tech University
National Institute of Standards and Technology
University of Illinois at Urbana-Champaign (Coordinated Science Lab and Material Science & Engineering)
TP02.01: Novel Thermal Methods and Applications
Monday AM, November 26, 2018
Sheraton, 3rd Floor, Fairfax AB
8:00 AM - TP02.01.01
Heat Capacity Determination—Tricks of the Trade
Mary Anne White1
Dalhousie University1Show Abstract
Sometimes very accurate heat capacity data are required; an example would be for the calculation of a thermodynamic cycle that involves small differences between large numbers. Sometimes less accurate data would still be useful, especially if they can be acquired quickly. In this talk, some instances of each situation will be presented, along with tips to attain high-accuracy data using relaxation calorimetry, moderate accuracy with using DSC, and quantitative estimates using other means.
8:30 AM - TP02.01.02
The Boiling Temperature of Ionic Liquids—An Experimental Approach
Christoph Schick1,2,Amir Abdelaziz1,Sergey Verevkin1
University of Rostock1,Kazan Federal University2Show Abstract
The very low vapor pressure of ionic liquids is challenging to measure. At elevated temperatures the liquids might start to decompose, at relatively low temperatures the vapor pressure becomes extremely low to be measured by conventional methods. We developed a highly sensitive method for mass loss determination at temperatures starting from 350 K up to 800 K. The technique is based on fast scanning (10 000 K s-1) and an alternating current (AC) calorimeter equipped with a chip sensor, that consists of a free-standing SiNx-membrane (thickness < 1 µm) and a measuring area with lateral dimensions of the order of 100 μm. A small droplet (diameter ca. 300 µm) of an ionic liquid is vaporized isothermally from the chip sensor in a vacuum-chamber. The surface-to-volume-ratio of such a droplet is large and the relative mass loss due to evaporation is therefore easy to be monitored by the changing heat capacity (J K-1) of the remaining liquid. The vapor pressure is determined from the measured mass loss rates using the Langmuir equation. The method was successfully tested with determination of vapor pressures and the vaporization enthalpy of the archetypical ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm][NTf2]). The created in this way data set in the extremely broad temperature range 358 K to 780 K has allowed estimation of the boiling temperature of [EMIm][NTf2]. The value (1120 ± 50) K should be considered as the first reliable boiling point of this ionic liquid obtained from experimental vapor pressures measured in the most possible close proximity to the normal boiling temperature.
Ahrenberg, M., M. Brinckmann, J. W. P. Schmelzer, M. Beck, C. Schmidt, O. H. Keßler, U. Kragl, S. P. Verevkin and C. Schick (2014). "Determination of volatility of ionic liquids at the nanoscale by means of ultra-fast scanning calorimetry." Physical Chemistry Chemical Physics 16(7): 2971-2980.
Neise, C., C. Rautenberg, U. Bentrup, M. Beck, M. Ahrenberg, C. Schick, O. Keßler and U. Kragl (2016). "Stability studies of ionic liquid [EMIm][NTf2] under short-term thermal exposure." RSC Advances 6(54): 48462-48468.
Ahrenberg, M., M. Beck, C. Neise, O. Keßler, U. Kragl, S. P. Verevkin, C. Schick (2016). "Vapor Pressure of Ionic Liquids at Low Temperatures from AC-chip-calorimetry." Physical Chemistry Chemical Physics 18(31): 21381-21390.
9:00 AM - TP02.01.03
Liquid to Glass/Crystal Transitions in Ionic Liquids Studied by Fast Thermal Conductivity Measurements
Carlos López-Bueno1,David Bugallo Ferrón1,Víctor Leborán1,M.C. Giménez-López1,Francisco Rivadulla1
Centro de Investigación en Química Biolóxica e Materiais Moleculares (CIQUS)1Show Abstract
We have developed an experimental setup for the simultaneous measurement of the thermal conductivity and heat capacity of liquids. This system is an extension of the 3ω method  capable to measure a sample volume of the order of ≈500 nL, which is an important advantage for the characterization of nanofluids, in which having a large amount of sample is sometimes difficult to achieve . The setup is designed for fast measurements during a thermal ramp, which along with the extremely small volume required allows the possibility of using it in a cryostat for analysing the temperature dependence of the thermal conductivity in a variety of fluids, across phase transitions, kinetic studies, etc.
Particularly, in this work we will present the study of the low temperature thermal and electrical conductivity of different ionic liquids around their liquid-to-solid transition. Using these methods we are able to identify a spinodal decomposition temperature in in 1-Ethyl-3-methylimidazolium trifluoromethanesulfonate (EMIM+ TfO-) around 150K. Below this temperature, the glassy phase is unstable against the formation of a crystalline phase in the whole system. This produces a 30% variation in the thermal conductivity of the system, depending on the thermal history. We discuss the possibility of using ionic liquids as configurable models to study the low temperature thermal conductivity of ionic solids.
 David G. Cahill, Review of Scientific Instruments, 1990, 61:2, 802-808.
 C. López-Bueno, D. Bugallo, V. Leborán and F. Rivadulla, Phys. Chem. Chem. Phys., 2018, 20, 7277-7281.
This work was supported by the Ministry of Science of Spain (Projects No. MAT2016-80762-R), the Consellería de Cultura, Educación e Ordenación Universitaria (ED431F 2016/008, and Centro Singular de Investigación de Galicia accreditation 2016-2019, ED431G/09), the European Regional Development Fund (ERDF), the Xunta de Galicia and the European Union (European Social Fund- ESF).
9:15 AM - TP02.01.04
Nanocalorimetric Investigation of the Gradient Effect on Nucleation in Thin Films
Shane Arlington1,Feng Yi2,David LaVan2,Timothy Weihs1
Johns Hopkins University1,National Institute of Standards and Technology2Show Abstract
The fabrication of many multiphase alloys, particularly in thin film systems, relies upon the nucleation of intermetallic precipitates within a solid solution. These films frequently contain sharp composition gradients which are not accounted for under Classical Nucleation Theory but are predicted to have a significant effect on the nucleation of new phases. Previous nanocalorimetric studies of Al3Ni formation in nanoscale Al-Ni multilayers indicate that interdiffusion must reduce the composition gradient prior to nucleation of the Al3Ni product phase, while molecular dynamics simulations show that gradients can impede nucleation in both the liquid and solid state in the Al-Ni system. Here, we investigate the gradient effect directly by controlling the as-deposited gradient in amorphous thin films. We deposit amorphous binary metallic films with controlled composition gradients through their thickness, where the average composition of the films matches a stable intermetallic phase. We heat the films with nanocalorimeters, using a wide range of heating rates, and we assess the impact of the composition gradients on nucleation through kinetic analysis. Isoconversion analysis is performed on the nanocalorimetric dataset to evaluate the effective activation energy as a function of extent of conversion. Extensive ex situ characterization is performed before and after reaction to assess the structural and compositional nature of the films and the crystallites formed. Future work will include in situ TEM investigations of the gradient effect during isothermal crystallization of graded and non-graded films.
9:30 AM - TP02.01.05
Abrupt Size Effect Observed in Layered Materials Below Critical Size—Linking Thermal Analysis with Local Structural Analysis
Zichao Ye1,Lito De la Rama1,Mikhail Efremov2,Andre Sutrisno1,Leslie Allen1
University of Illinois at Urbana-Champaign1,University of Wisconsin–Madison2Show Abstract
Materials often exhibit exotic properties because of “discrete regions”, regions that have different chemical environment from the remaining part of the system. Material at the first level is treated as a uniform “bulk” with single sets of intrinsic and extrinsic characteristics; the next level incorporates finer details of the system by segmenting it with discrete regions, including interfaces (e.g., lamella mating boundaries), surfaces (e.g. nanoparticle spheres) and defects (e.g., gauche kinks). The effect of these discrete regions is highlighted by material miniaturization. At extremely small scale lengths (<10 nm), properties of the “whole” object (e.g., melting, lattice structure, bandgap, conductivity, optical) are dominated by the nature of “local” discrete regions. Regular thermal analysis using calorimetry has no depth perception – it only yields average thermodynamic values, whereas NMR has the unique capability to probe the local structure of each individual atom. Here we link calorimetry (NanoDSC or DSC) thermal analysis with 13C NMR structural analysis to report an abrupt bulk-to-discrete transition in 2D layered silver alkanethiolate (AgSCn, n=1-16) with a critical chain length of n=7. None of the carbon group share identical chemical environment below the critical length, making AgSCn (n=2-6) uniquely different materials, even though the crystal structures of all AgSCn are preserved throughout. Extraordinary changes of thermodynamic properties, including ~500% increase of melting enthalpy and ~50oC increase of melting point, are also observed at the bulk-to-discrete transition. This transition is universal for aliphatic layers, including n-alkanes with a critical chain length of n=11. A new 3D spatial model is constructed to divide the aliphatic chains of AgSCn into three bulk or discrete segments: (a) tail segment that forms interlayer interfaces, which are never planar structures but have 3D depth; (b) head segment that is strongly affected by the metallic core; (c) bulk mid-chain segment which shows similar properties to the hydrocarbon chains in polyethylene. The presence (multilayer) or absence (1-layer) of odd/even effect is exclusively attributed to the nature of the localized tail segment. Bulk-to-discrete transition occurs when material properties are dominated by the discrete head and tail segments over the bulk segment at/below critical length. This work is seminal to the design of novel aliphatic lamellae with tailorable properties and has applications in molecular electronics and biophysics.
10:30 AM - TP02.01.06
Phase Transformations in CuZr-Based Shape Memory Thin Films Analyzed by Combinatorial Nanocalorimetry
Joost Vlassak1,Mark Miao1
Harvard University1Show Abstract
We have investigated the phase transformations in sputtered CuZr-based shape memory thin films using a combinatorial nanocalorimetry technique that is capable of making differential calorimetric measurement on thin-film samples with a sensitivity as small as 12 pJ/K. We first investigate the crystallization kinetics of amorphous as-deposited equiatomic CuZr samples and demonstrate non-Arrhenius diffusion kinetics that is well described using a phenomenological model based on the fragility of super-cooled liquids. We then explore the conditions for the formation of the martensitic phase responsible for the shape memory properties of this alloy. We will show that fast, low-temperature cycling through the martensitic transformation increases the hysteresis, which we attribute to the accumulation of defects during the martensitic transformation. If, however, the austenitic phase is given sufficient time at elevated temperature to annihilate these defects, the transformation is stable under thermal cycling conditions. The addition of Ni to the CuZr alloy raises the martensite transformation temperature making it a potential high-temperature shape memory alloy. The microstructures of select CuZrNi samples have been analyzed using XRD and cross-sectional TEM. We will present the effects of composition, heat treatment, and grain size on the transformation temperature, hysteresis, and functional stability of the samples. We will also demonstrate that under certain conditions the martensitic transformation proceeds in an explosive fashion. The transformation behavior of these alloys will be discussed in light of ab initio simulations of the materials system.
11:00 AM - TP02.01.07
Physical Limits of Laser Gold Nanowarming
John Bischof1,Kanav Khosla1,Li Zhan1,Aditya Bhati1,Aiden Carley-Clopton1,Mary Hagedorn2,3
University of Minnesota Twin Cities1,Smithsonian National Zoological Park2,University of Hawaii3Show Abstract
In this work we explore the physical limits of a new technique to rewarm vitrified droplets and zebrafish embryos impregnated with 1064 nm resonant gold nanorods that are irradiated by a Nd:YAG ms pulsed laser. Importantly, the droplets and the embryos loaded with 2 M PG are first cooled by a modified cryotop at rates estimated to be 90,000 °C/min to a visually transparent state in liquid nitrogen. Numerical modeling demonstrates possible differences in warming depending on full mixing (droplets) vs. micro-injection into the yolk of the zebrafish. Experimental measurments based on optical transparency vs. cloudy behavior are then used to judge the physical success of the procedure. From this we present a map of the successful laser power, pulse length, CPA concentrations and gold concentrations that can yield physical success for laser gold nanowarming.
11:30 AM - TP02.01.08
Non-Contact Thermal Analysis with Fast and Micro-Scale Thermographical Imaging
Tokyo Institute of Technology1Show Abstract
Non-contact quantitative thermal imaging in micro-scale is attractive to realize the non-contact thermal analysis. It visualizes not only the typical thermal analysis on phase transitions and thermal degradation, but also the heat transfer. We propose a system of infared camera equipped with an original optics and temperature calibration algorithm, which enables to achieve the high-quality and fast-speed thermal imaging. The Infrared (IR) optical lens design has been optimized to each wavelength band of the photon type and the thermal type detectors of IR FPA. Typical applications to observe the freezing biological cells and the crystallization of organic molecular crystals are reviewed. Combined with the techniques of microscale flying spot laser and the superimpose processer, the method is applied to determine the heat transport properties. The recent instrumentation of thermospectroscopy and the high temperature imaging systems are also introduced.
11:45 AM - TP02.01.09
Time-Domain Transient Fluorescence Spectroscopy for Thermal Characterization of Polymers
Yanan Yue1,2,Hao Wu1,Yangheng Xiong1,Xin Zhang2
Wuhan University1,Boston University2Show Abstract
In this work, a time-domain fluorescence spectroscopy technique is developed to characterize thermophysical properties of polymers. The method is based on fluorescence thermometry of materials under periodic pulse heating. In the characterization, a continuous laser (405 nm) is modulated with adjustable periodic heating and fluorescence excitation. The temperature rise at sample surface due to laser heating is probed from simultaneous fluorescence spectrum. Thermal diffusivity can be determined from the relationship between normalized temperature rise and the duration of laser heating. To verify this technique, thermal diffusivity of a polymer material (PVC) is characterized as 1.031×10-7 m2/s, agreeing well with reference data. Meanwhile, thermal conductivity can be obtained by the hot plate method. Then, both steady and unsteady thermophysical properties are available. Quenching effect of fluorescence signal in our measurement can be ignored, as validated by longtime laser heating experiments. The uncertainty induced by uniformity of laser heating is negligible as analyzed through numerical simulations. This non-destructive fluorescence-based technique does not require exact value about laser absorption and calibration experiment for temperature coefficient of fluorescence signals. Considering that most polymers can excite sound fluorescence signal, this method can be well applied to thermal characterization of polymer-based film or bulk materials.
TP02.02: Thermal Properties of Polymers and Biomaterials
Monday PM, November 26, 2018
Sheraton, 3rd Floor, Fairfax AB
1:30 PM - TP02.02.01
Fast Scanning Calorimetry of Silk Protein
Tufts University1Show Abstract
Silk is a naturally occurring biopolymer used in textiles for over 5000 years. The properties of the B. mori silk protein, fibroin, are related to its secondary structures, such as helices, random coils, turns, and beta pleated sheet crystals. We have prepared fibroin by extracting it from the native cocoons and use this as a starting material for our investigations into the polymorphic structure of the protein. Using infrared spectroscopy and heat capacity measurements, we quantify the amounts of the different secondary structures. By varying processing treatments, two crystalline polymorphs, Silk I and Silk II, can be formed and their structure and properties studied using X-ray diffraction and fast scanning calorimetry (FSC). Silk degrades before melting when heated at slow rates. With FSC, we heat silk at 2000 K/s, thereby minimizing effects of thermal degradation. We show that beta pleated sheet crystals melt to form unstructured non-crystalline fibroin protein, upon the input of heat energy alone. We show that Silk I crystals melt at (565 ± 14) K, while Silk II crystals melt at (624 ± 11) K. A general method for using FSC to estimate the thermodynamic heat of fusion is presented, and demonstrated for the beta pleated sheet crystals. The FSC methods developed here for the study of silk are readily transferable to studies of other crystalline materials, such as synthetic polymers, amino acids, and proteins.
2:00 PM - TP02.02.02
Thermal Transport and Flow in Polymeric Materials
David Venerus1,2,David Nieto Simavilla2,Andy Kiessling2,Jay D. Schieber2
The strong coupling of mechanical and thermal effects in polymer processing flows has profound implications on both the processability and final properties of the material. Simple molecular arguments suggest that Fourier’s law must be generalized to allow for anisotropic thermal conductivity in deforming polymeric materials. In addition, theoretical results suggest a linear relationship between the thermal conductivity tensor and the stress tensor, or a stress-thermal rule. Using a novel optical method based on Forced Rayleigh Scattering (FRS) developed in our laboratory, we obtain quantitative measurements of all components of the thermal diffusivity tensor in polymers subjected to deformation. These data have been used to carry out the first (and only) tests of the stress-thermal rule, which we have found to be valid for several polymer chemistries in both shear and elongational deformations. More recently, we have developed a novel technique based on Infrared Thermography (IRT) that complements FRS and allows for the study of a wider range of polymeric materials. The IRT technique also allows us to investigate the dependence of heat capacity on deformation. These experiments are used to develop an understanding of the molecular mechanisms of thermal transport in polymers that are essential for the development of advanced materials.
2:15 PM - TP02.02.04
Utilizing Fast-Scan Calorimetry on Polymer Crystallization and Melting with Gibbs-Thomson, Hoffman-Weeks and Thermal Gibbs-Thomson Plots
Hiroshima University1Show Abstract
Crystallization and melting behaviors of chain-folded polymer crystals are examined by fast-scan calorimetry (FSC) combined with other various methods including small angle X-ray scattering (SAXS) with Gibbs-Thomson, Hoffman-Weeks, and thermal Gibbs-Thomson plots, which offer new insights on polymer crystallization mechanism. The melting point of lamellar crystals formed isothermally at Tc was measured by FSC and calibrated in terms of the heating rate dependence on the basis of the modeling of melting kinetics for the determination of the melting point at zero heating rate TM. By combining TM with the crystalline lamellar thickness dc determined by SAXS, the Gibbs-Thomson (G-T) plots of TM and Tc against (dc)-1 are utilized for the determination of the equilibrium melting point of chain-extended infinite-size crystal TM0. The Hoffman-Weeks (H-W) plot of TM against Tc is an alternative method of TM0 determination. For many polymers, both of the plots, especially the G-T plots, are curved. In order to understand the meaning of the curved G-T and H-W plots, we propose a thermal Gibbs-Thomson plot in terms of the melting point TM and the total heat of fusion ΔHf in the secondary stage of isothermal crystallization, during which thickening and perfecting of lamellar crystals undergo and bring the shift in both of TM and ΔHf with longer annealing time.
2:45 PM -
3:30 PM - TP02.02.05
Thermal Properties and Structure of Electrospun Blends of PVDF and Fluorinated Copolymers
Nelaka Govinna1,Ilin Sadeghi1,Ayse Asatekin1,Peggy Cebe1
Tufts University1Show Abstract
We report a study of the structure and thermal properties of blends comprising poly(vinylidene fluoride), PVDF, and a random copolymer of poly(methyl methacrylate) and 1H,1H,2H,2H-perfluorodecyl methacrylate, which are candidates for applications as superoleophilic membranes for oil-water separation. Blend composition was systematically varied by controlling the PVDF-to-copolymer ratio. The role of processing method and copolymer content on structure and properties was investigated for both fibers and films. Non-woven fibrous membranes were obtained by electrospinning (ES) solutions of PVDF and copolymer, at 20% w/v in a mixed solvent, N,N-dimethylacetamide/acetone (1/1 v/v). Scanning electron microscopy showed that bead-free fibers were obtained at all compositions. Fiber diameter ranged from 0.4 μm – 1.9 μm, and thinner fibers were obtained for PVDF content above 80 wt.%. As the copolymer content in the blends increased, the degree of crystallinity and the onset of degradation for each blend decreased while the glass transition temperature (Tg) increased, as evidenced by differentail scanning calorimetry (DSC), Wide-angle X Ray Scattering (WAXS) and thermogravimetry (TG) experiments. The variation of Tg followed the Kwei model of Tg mixing in polymer blends and suggest strong intermolecular interactions between the PVDF and copolymer molecules when the copolymer is present in large quantities, and relatively weaker interaction when the copolymer fraction is smaller than 0.15. Processing conditions had a greater impact on the crystallographic phase of PVDF than the copolymer content. For crystalline ES fibers, WAXS and infrared spectroscopy indicated only polar phases were present, and beta was dominant over gamma phase at all compositions. In comparison, solution cast films also contained polar phases, with an increase of gamma phase PVDF. Melt crystallized films formed non-polar alpha phase exclusively.
3:45 PM - TP02.02.06
The Unfolding and Refolding Properties of Proteins—A Case Study on Lysozyme
Tsinghua University1Show Abstract
Proteins, serving as the principal structural and functional units in living organisms, have highly ordered structures and conformations folded from peptide chains. When subjected to stress such as heat or chemicals, proteins may unfold. The unfolded peptide chains have the potential to refold when the stress factors are completely/partially removed. In this presentation, the unfolding/refolding behaviors of a model protein, lysozyme, are discussed in detail.
First, a method to differentiate the two-state and non-two-state unfolding of proteins is discussed. It is called an interruption-incubation protocol: protein solutions are incubated at different interrupting temperatures to allow the partial unfolding of the macro-molecules. Then the thermal behaviors of the proteins upon reheating are examined. Comparisons between lysozyme and a few other proteins including bovine serum albumin will be presented.
Second, the folding/unfolding behavior of lysozyme in the presence of micelles composed of the unstructured b-casein proteins will be presented. Depending on the b-casein/lysozyme molar ratio, a partially unfolded structure of lysozyme can occur. This partially unfolded state of lysozyme loses most of its tertiary structure and, after heating, the denatured lysozyme molecules are trapped in the charged coatings of b-casein micelles and cannot refold upon cooling. The thus obtained protein complex can be viewed as a kind of special polyelectrolyte complex micelle.
Third, the unfolding/refolding behavior of lysozyme in the presence of a negatively charged polyelectrolyte sodium poly(styrenesulfonate) or PSS will be presented. With elevated PSS concentration, a new state (state I) is first formed via a “two-state” conversion process and this state can further convert to a completely unfolded state (state II) via a “non-two-state” conversion mechanism.
Finally, the mutual influence of lysozyme and lipid liposomes consisting of neutral and negatively charged phospholipids on their thermal behaviors will be presented. Interestingly, the enrichment of the negatively charged lipids cannot be induced by the native and ex situ unfolded (unfolded in the absence of liposomes) lysozyme, but requires that lysozyme undergo an in situ unfolding process (unfolding in the presence of liposomes).
4:15 PM - TP02.02.07
A Novel Approach to Evaluate Microorganism Viability and Microbial Growth Using the Highly Versatile Heat-Transfer Method (HTM)
Kai Betlem1,Mikhajlo Zubko1,David Sawtell1,Bart van Grinsven2,Thomas Cleij2,Peter Kelly1,Marloes Peeters1
Manchester Metropolitan University1,Maastricht University2Show Abstract
The Heat Transfer Method (HTM) is a novel, versatile and low-cost thermal technique that has already shown its use in the analysis of (biological) targets ranging from small molecules, to DNA, to whole cells and bacteria. The surface can be functionalized with specific receptors (DNA, polymers) for measurements and is the central element through which the heat flux will pass. The internal temperature of the heat sink, T1, is measured by a thermocouple and steered via a controller, which is connected to a power resistor. The front side of the chip is exposed to the liquid, where T2 is measured at the solid−liquid interface. To extract the heat-transfer resistance Rth (°C/W) quantitatively, the ratio of the temperature difference ΔT = T1 − T2 and the input power P according to Rth = ΔT/P, is analysed. Changes at the interface will reflect in a difference in the overall thermal resistance1.
Here, we report a novel application for the HTM with the real-time viability study of microbes, using yeast (Saccharomyces cerevisiae) as a model organism. To accompany this study, the existing flow cell was redesigned, preventing the build-up of gasses produced in the metabolic cycle yeasts, leading to an increase of the Rth signal corresponding with the increasing concentration of cells in the flow chamber. Therefore, it was possible to discriminate between a wild type strain (DLY640) and a temperature sensitive mutation (cdc13-1) based on the growth kinetics. At temperatures higher than 30 °C the mutant strain stops growing2. This corresponds to a decrease in temperature of the optimal growth rate of the cells compared to wild type yeast cells.
The influence of factors inhibiting the replication process of yeast cells can be followed in real- time using this technique. Here, the signal increase in the thermal resistance under normal growth conditions seized when changing to a growth medium depleted of nutrients, the introduction of a toxic component (Cu2SO4) or application of a thermal shock treatment. Upon restoring the normal conditions, only the nutrient depleted condition remained viable, in all other situations the yeast cells where permanently eliminated. These results were confirmed by classical plating experiments of yeasts that were exposed to the same conditions as during the HTM measurement.
Having the advantages of simplicity, signal processing and portability, the setup can be used on site without requiring a lab environment. The described methodology is versatile and can be adapted to study different antimicrobial properties, such as the response to antibiotics on a wide range of different microbes.
1. B. van Grinsven, K. Eersels, M. Peeters, P. Losada-Pérez, T. Vandenryt, T. Cleij and P. Wagner, ACS Applied Materials & Interfaces, 2014, 6, 13309-13318.
2. K. Betlem, S. Hoksbergen, N. Mansouri, M. Down, P. Losada-Pérez, K. Eersels, B. van Grinsven, T. Cleij, P. Kelly, D. Sawtell, M. Zubko, C. Banks and M. Peeters, Physics in Medicine, (Accepted) 2018.
4:30 PM - TP02.02.08
Determination of the Thermophysical Properties of Nucleobases with Fast Scanning Calorimetry
Amir Abdelaziz1,Dzmitry Zaitsau1,Sergey Verevkin1,Christoph Schick1,2
Rostock University1,Kazan Federal University2Show Abstract
The determination of the thermophysical properties, e.g. fusion temperature, fusion enthalpy, sublimation enthalpy and vapour pressure lay within focus of many scientific fields and industrial applications. These values are directly connected to the intermolecular forces in crystal state, provides the lattice energy, change in ordering by going from crystal to gas phase and the solubility properties of organic molecules.
In many cases investigation of thermally labile systems e.g. biomolecules at slow heating rates are accomplished with low thermal stability of them. The application of classic techniques to measure their thermophysical properties often fails, making the estimation of the corresponding thermodynamic parameters, like melting temperature, enthalpy of fusion, vapor pressure highly inaccurate or even impossible.
In the present study, fast scanning calorimetry was successfully applied for determination of the sublimation vapour pressure, enthalpies of sublimation and melting behaviour of the nucleobases cytosine, thymine, adenine, uracil and guanine, the building blocks of DNA and RNA, which are known to decompose at high temperature.
TP02.03: Poster Session I
Monday PM, November 26, 2018
Hynes, Level 1, Hall B
8:00 PM - TP02.03.02
Noncontact Thermophysical Property Measurements of Molten Oxides by Electrostatic Levitation Furnaces Onboard International Space Station
Koyama Chihiro1,Haruka Tamaru1,Hideki Saruwatari1,Masato Ohshio1,Hirohisa Oda1,Yasuhiro Nakamura1,Takehiko Ishikawa1
Japan Aerospace Exploration Agency1Show Abstract
Electrostatic levitation furnaces are capable to measure thermophysical properties of chemically reactive materials such as liquids of refractory metals, alloys, and oxides1. Since the furnaces can levitate the liquids by using Coulomb force, the liquids are not contaminated and nucleated from containers. Thus, the thermophysical properties are precisely measured under wide temperature range including undercooling range. Among the properties, we have been measuring density, viscosity, and surface tension of melt with high melting temperature (Tm). On the ground our group measured thermophysical properties of various kind of molten metals including W, Re, and Ta (Tm ≈ 3500 K) which are difficult to measure them in an crucible2. However, the measurements of molten oxides were scarcely performed on the ground, because oxides are difficult to charge and then do not levitate. In order to resolve this problem and measure physical properties of oxides, our group designed and fabricated the Electrostatic Levitation Furnace onboard the ISS (ISS-ELF) 3which enables to levitate oxides with small charge due to an effect of microgravity.
To measure molten density, one of the fundamental thermophysical properties, the capabilities of levitation and heating were checked by using Al2O3. As a result, each sample levitated and melted fully in dry air by four semiconductor lasers. During cooling the melt, the temperature was measured by a pyrometer. The sample images were recorded by using CCD camera and UV-light. From the image and weight after the measurement, the density was calculated. The density as a function of temperature shows good agreement with that obtained by Langstaff et al. (2013)4 using aerodynamic levitator. It also shows about 2 % lower than our earlier results obtained by using electrostatic levitator on the ground in high vacuum condition (Paradis et al. 2004)5. This result proves the validity of the density measurement with the ISS-ELF. The functional check for the surface tension and viscosity measurement is being currently conducted, and detailed results will be reported later.
1. Rhim, W.-K., Chung, S. K., Barber, D., Man, K. F., Gutt, G., Rulison, A., Spujt, R. E, Rev. Sci. Instrum. 64, 2961-2970 (1993)
2. Ishikawa, T., Paradis, P.-F. in High-Temperature Measurements of Materials, ed. by Fukuyama, H and Waseda, Y (Springer Berlin Heidelberg 2009) P. 173-195
3. Tamaru, H., Ishikawa, T., Okada, J.T., Nakamura, Y., Ohkuma, H., Yukizono, S., Sakai, Y., Takada, T., Int. J. Microgravity Sci. Appl. 32, 32104 (2015)
4. Langstaff, D., Gunn, M., Greaves, G. N., Marsing, A., Kargl, F., Rev. Sci. Instrum. 84, 124901 (2013)
5. Paradis, P.-F., Ishikawa, T., Saita, Y., Yoda, S. J. J. Applied Physics 43, 1496 – 1500 (2004)
8:00 PM - TP02.03.03
Properties of Poly(Ethylene Terephthalate) Electrospun Fibers Containing Carbon Nanotubes or Graphene
Andrew Clark1,Peggy Cebe1
Tufts University1Show Abstract
Electrospinning is a process used to create polymer fibers with diameters on the order of nanometers to microns. Blending polymers with nanomaterials, such as carbon nanotubes or graphene, to create nanocomposites can improve the thermal, mechanical and electrical properties of the host polymer. In this study, we investigate the effects of blending carbon-based fillers on the structural and thermal properties of electrospun fibers of poly(ethylene terephthalate). PET fiber solutions containing 1.0 wt.% multi-walled carbon nanotubes (MWCNTs) or graphene flakes were electrospun from hexafluoroisopropanol. The fibers were characterized structurally using wide angle X-ray scattering, infrared spectroscopy, and scanning electron microscopy. Thermal properties were studied using thermogravimetry and temperature modulated differential scanning calorimetry (TMDSC). Fiber diameters ranged from 670 to 900 nm. WAXS revealed that the as spun homopolymer as well as the composites containing 1.0 wt% of MWCNTs or graphene were amorphous. Prior to thermal analysis the fiber mats were dried at 85 oC for 20 minutes to evacuate any solvent, as well as minimize effects due to fiber shrinkage. Addition of the MWCNTs or graphene resulted in a modest decrease of the glass transition and cold crystallization temperatures. Quasi-isothermal TMDSC of the dried fiber mats reveals less mobile amorphous fraction in the blends. MWCNT-based composites had mobile amorphous fraction of 0.83 while graphene-based composites and neat PET fibers had 0.89 and 0.91, respectively. Cold crystallization during QI-TMDSC increased the solid fractions of the MWCNT composite, graphene composite and neat fibers to 0.53, 0.50 and 0.43 respectively. Future work will include investigation of the fiber composites using broadband dielectric spectroscopy.
8:00 PM - TP02.03.04
Cyclic Phase Transformation Behavior in Shape Memory Zirconia—Single Crystals vs Polycrystals
Isabel Crystal1,Alan Lai1,Christopher Schuh1
Massachusetts Institute of Technology1Show Abstract
In shape memory materials, cyclic martensitic phase transformation can accumulate damage over many cycles due to the mismatch stresses developed amongst the phases and grains. Reducing such mismatches improves the cyclic performance, as known in brittle Cu-based shape memory alloys, where structures with relatively fewer grains (i.e. oligocrystalline or single crystalline specimens) exhibit better cycling properties than conventional polycrystals. The purpose of the present work is to assess this approach in zirconia-based ceramic systems, which are attractive for their high temperature capabilities and higher transformation stresses than shape memory metals, yet are also known to be brittle and experience fracture during the martensitic transformation. Specifically, this work compares tetragonal-to-monoclinic transformation behavior of polycrystalline and single crystalline samples of yttria-doped zirconia compositions. The evolution of transformation enthalpies and strains as well as sample mass and integrity are measured to characterize thermal cycling performance. Microscopic examination also provides insight into microstructural changes after repeated transformation.
8:00 PM - TP02.03.05
The Shape Memory Effect in Polymer Systems Based on PMMA/PEG and Epoxy DGEBA / D230
Kátia Furlani1,Ruben Rodríguez1
State University of Northern Fluminense1Show Abstract
Shape memory polymers (SMPs) are materials considered to be intelligent due to the ability to be programmed to fix a temporary shape and subsequently regain their original shape after the application of an appropriate stimulus. They have been studied by researchers in different fields such as chemistry, materials engineering, mechanics, biomedical sciences, and microelectronics engineering. In addition to the benefits cited, they are low cost, easy to process and can have their properties easily modified through the combination with other chemical compounds, in order to expand the field of application, taking into account the needs of the market and favoring the technological advances. In this work, we analyze and compare the thermally induced shape-memory effect (SME) of two different polymer systems, one being a thermoplastic formed by a semi-interpenetrating network of poly (methyl methacrylate) and poly (ethylene glycol) (PMMA / PEG), and the other thermosetting based of the DGEBA epoxy resin (DER 331) using the aliphatic amine Jeffamine D230 (DGEBA / D230). Each material was characterized according to its ability to deform, fix a temporary shape and recover, as well as response time and life cycle, which corresponds to the number of consecutive cycles that can be performed without failure. PMMA/PEG exhibited higher deformation rate and shape fixation, but DGEBA/D230 showed higher recovery rate and shorter response time. The differentiated behavior in the analyzed systems is directly associated to the molecular structure. The higher DGEBA / D230 cross-linking density allows for faster and more efficient response, but PMMA / PEG thermoplasticity is vulnerable to long-range molecular chain slippage.
8:00 PM - TP02.03.06
Thermal Sensing with Luminescent Nanothermometers Operating in the Near-Infrared
Pascal Gschwend1,Fabian Starsich1,Sotiris Pratsinis1
ETH Zurich1Show Abstract
Temperature measurements are fundamental in countless industrial and research applications. As the focus shifts towards small scale applications such as temperature measurements in microelectronics or nanomedicine, tranditional contact methods (thermistors, thermocouples) are not applicable. Therefore, nano-scale thermometers with high spatial resolution are needed.
Luminescence thermometry is a simple and inexpensive approach to remotely measure temperatures in real time with high accuracy and good spatial resolution. Here, a ratiometric approach for luminescent nanothermometry is presented on the example of BiVO4 nanoparticles  codoped with Nd3+ and La3+, which operate in the near-infrared window ideal for applications in biological tissue. The effect of La3+ codoping on the structural and luminescent properties of BiVO4:Nd3+ is investigated and an optimal composition is found. Most importantly, through careful choice of excitation wavelength and close analysis of the emission peaks of these luminescent nanocrystals, a relative thermal sensitivity of up to 1.44 %/K was achieved, leading to temperature uncertainties down to 0.27 K. Finally, the merit of the proposed nanothermometer was demonstrated ex vivo within biological tissue proving the feasibility of BiVO4:Nd,La for non-invasive thermometry with high spatial resolution.
: Brites CDS, Millan A, Carlos LD, Lanthanides in Luminescent Thermometry: Elsevier, 2016. Handbook on the Physics and Chemistry of Rare Earths; No. 49
: Brites CDS, Lima PP, Silva NJO, Millan A, Amaral VS, Palacio F, Carlos LD. Organic-Inorganic Eu3+/Tb3+ Codoped Hybrid Films for Temperature Mapping in Integrated Circuits. Frontiers in Chemistry. 2013;1
: Starsich FHL, Gschwend P, Sergeyev A, Grange R, Pratsinis SE. Deep Tissue Imaging with Highly Fluorescnet Near-Infrared Nanocrystals after Systematic Host Screening. Chemistry of Materials, 29, 2017, 8158-8166
8:00 PM - TP02.03.07
Enhanced Gel Electrophoretic Separation of DNAs with Dynamically Controlled Photothermal Temperature Gradient by Digital Micromirror Device
Weike Hu1,Sichao Hou1
Northeastern University1Show Abstract
Uncontrolled temperature variation in gel electrophoresis is often considered pestiferous to separation. This article describes a temperature gradient enhanced gel electrophoresis, where a controlled temperature gradient is generated inside agarose gel via photothermal effect to modulate the separation of DNA molecules. The temperature gradient generated by digital micromirror device can be discretionally patterned in both static and dynamic modes to achieve steady-state and transient thermal control. Curved separation bands have been observed in the temperature gradient for double-strand and single-strand DNAs. Compared to gel electrophoresis without gradient, the separation capability of a gel at a temperature gradient of 20 to 60 °C over 10 cm is raised up to 205% for 20 kbp DNA fragments. The enhanced separation is due to larger pore size of the gel at higher temperature, which will reduce diffusion resistance and increase migration rate. Theoretical analysis confirms that diffusion rate is proportional to temperature to the third power. Given the easiness and spatial flexibility of light modulation, the photothermally generated temperature gradient can be a powerful way to enhance separation capability of a given gel in electrophoresis.
8:00 PM - TP02.03.08
Remote Thermal Imaging For High Throughput Materials Thermal Characterization
Jingwen Liu1,Sichao Hou1,Ming Su1
Northeastern University1Show Abstract
Thermal physical properties of materials are often characterized at low throughput. We report here the new use of infrared imaging system for high throughput, remote and non-destructive characterization of materials. The high temporal and spatial resolutions of infrared imaging allow temperatures of multiple samples to be simultaneously examined to derive the temperature dependent thermal conductivity of metal plate and along various crystal orientation, as well as to derive the temperature and enthalpy change related to phase change in organic phase change materials.
8:00 PM - TP02.03.09
Thermal Stability and Microstructural Behavior of Sintered Iron Oxide Nanoparticles
Josiane Souza1,Edson Leite1,Júlio César Sczancoski1
Federal University of São Carlos1Show Abstract
Iron oxide (Fe2O3) is one of the most abundant compounds in nature. This material has four well-known crystalline polymorphs, which exhibit different structural arrangements and physicochemical properties. These particular features have driven the use of this oxide for technological applications in water splitting, gas sensors, lithium-ion batteries, and magnetic storage devices. A fundamental concept is that controlling the thermal stability as well as final microstructure of Fe2O3 at nanoscale is possible to tailor its electric and magnetic properties. Hence, the aim of our study was focused on the thermal behavior of Fe2O3 nanoparticles previously grown via hydrothermal reactions at 160 C for 8 h. These nanoparticles were pressed and conformed as pellets (green compact), which were sintered in a dilatometer (DIL) by using a temperature range from 30 °C to 1300 °C under argon atmosphere. This analysis revealed a size-dependent sintering mechanism, since these nanoparticles presented a lower densification temperature (≈ 750 °C) than Fe2O3 microparticles synthesized by other conventional routes (≈1300 °C). In order to monitor the strengthening of the microstructure (neck growth between particles), densification (removal of porosity accompanied by shrinkage), and coarsening (grain growth and/or pore growth), other Fe2O3 pellets were sintered in the DIL at 750 °C for 12 h and 900 °C for 1 min, respectively. In this case, both presented relative densities ranging from 50% to 80%. On the other hand, scanning electron microscopy (SEM) images indicated the presence of several grain grown containing interconnected porous. For pellets sintered at 900 °C for 1 min, X-ray diffraction patterns were indexed to α-Fe2O3 phase, while at 750 °C for 12 h was identified a mixture of α-Fe2O3 and Fe3O4. Magnetite - cubic structure and hematite - rhombohedral structure. The existence of adsorbed water and organic compounds were detected by means of differential thermal analysis and thermogravimetry. These substances were able to affect the mass transport and densification process in Fe2O3 pellets.
8:00 PM - TP02.03.10
Thermal Transport in Soft PAAm Hydrogels
Ni Tang1,Zhan Peng1,Rulei Guo1,Meng An1,Xiandong Chen1,Xiaobo Li1,Nuo Yang1,Jianfeng Zang1
Huazhong University of Science & Technology1Show Abstract
As the interface between human and machine becomes blurred, hydrogel incorporated in electronics and devices have emerged to be a new class of flexible/stretchable electronic and ionic devices. The heat dissipation in the electronic devices involving hydrogels will be a serious concern if this trend continues. Thus, an in-depth understanding of the thermal conduction behaviors in hydrogels and hydrogels related devices are potentially a hot topic and have not yet been seriously explored, especially for pure hydrogels.
Here, we report the experimental measurement and simulations of thermal conductivity of polyacrylamide (PAAm) hydrogels for the first time. We show that the thermal conductivity of PAAm hydrogel can be modulated by its crosslinking density and water content. We also explore the underline mechanism that both the crosslinking density and water content attribute to thermal conductivity of hydrogels. Our study offers an excellent example for measuring and analyzing the thermal conduction behaviors of hydrogel's system. Furthermore, this work shows great significance in fundamental understanding of thermal transport in soft materials and provides design guidance for hydrogel-based devices.
8:00 PM - TP02.03.11
Thermally Insulating Oxide Films Synthesized on Aluminum Alloy(A5052) by Chelate Flame Method
Yanxin Dan1,Takashi Kosuda1,Atsushi Nakamura1,2,Keiji Komatsu1,Hidetoshi Saitoh1
Nagaoka University of Technology1,Chubu Chelest Co., Ltd2Show Abstract
Application of thermal barrier coatings (TBCs) on hot components of gas turbines enables increase in over all engine efficiency by either lowering the metal surface temperature or maintaining the existing metal surface temperatures by decreasing cooling air flow. The technology involves choices of materials and spatial configurations, as well as survivability upon extreme temperature cycling without loss of functionality. Currently, the preferred insulating oxide material of choice for TBCs is 6–8 wt% yttria-stabilized zirconia (YSZ), which exhibits metastable tetragonal (t′) form when applied on super alloy components by plasma spraying or by electron-beam physical vapor deposition. However, t′phase becomes increasingly unstable at high temperatures, it decomposes to a mixture of tetragonal (t) and cubic(c) phases, and transforms to monoclinic (m) phase at cooling processes, accompanied with excessive volume expansion, resulting in crack formation in TBCs. To cope with these requirements, alternate TBC’s materials are strongly required having higher temperature capability, better mechanical properties and lower thermal conductivity.
Thermal insulation performance of the material influences it’s thermal conductivity. The thermal conductivity can be controlled by film’s microstructure. The thermal conductivity of oxide films were decreased by increasing porosity. In this study, we propose a chelate flame method which is a method for obtaining an insulating oxide film from metal-ethylenediaminetetraacetic acid (EDTA) complex. We synthesized thick Er2O3 and Y2O3 films on aluminum alloy (A5052) from two types of metal-EDTA complexes (EDTA-Er-H and EDTA-Y-H) using a flame sprayer. The deposition of metal oxide in the proposed synthesis involves two mechanisms, namely, chemical reaction and physical collision. It begins with a chemical reaction in which metal–EDTA complex is decomposed and oxidized to form metal-oxide particles. Therefore, the properties of the deposited film depend on the temperature and velocity of the moving particles. It is the physical collision of the metal-oxide particles with the substrate happens, and forms a film as the accumulated layer of incident particles solidify. First, in order to optimize the fabrication conditions for TBCs, the adhesion between the A5052 and the oxide film was evaluated, and the splat morphology was investigated. Next, thick oxide films were synthesized on A5052 based on optimized synthesize conditions.
Although the Y2O3 film synthesized on A5052 was annealed close to the melting point of the A5052 substrate, it showed strong adhesion without delaminations. As results, the obtained Er2O3 having porosities of 3.8 to 23.3% film with thickness of 105-125 μm, and the Y2O3 film having porosities of 8.1 to 21.8% with thickness of 85-163 μm were fabricated on A5052 substrate. These results indicated that thick metal oxide films with various microstructures were fabricated by chelate flame method.
8:00 PM - TP02.03.12
Thermal and Spectral Analysis of Microencapsulated Leuco Dyes
John Sinko1,Donovan Bassett1,Danielle Hall1,Alexis Corbett1,Binit Sthapit1,Kannan Sivaprakasam1
St. Cloud State University1Show Abstract
Leuco dyes are phase-change materials that undergo characteristic thermal and spectral changes with temperature. These materials have the potential to contribute to energy savings by reducing the light absorption of structures at high temperatures. In this study, we characterized a set of microencapsulated leuco dyes with transitions at 20°C, 25°C, and 30°C. These materials were subjected to differential scanning calorimetry and thermogravimetric analysis to understand the thermodynamic behavior around the transition points. UV-Vis-NIR diffuse reflectance spectra were also collected under quasi-isothermal forced heating and cooling of coating samples. The thermal and spectroscopic results were compared as a function of temperature to establish the thermo-optical characteristics of the leuco dyes for application as energy capturing coating materials. Spectra of leuco dyes were also simulated and compared to the experimental data. The comparison of temperature-dependent optical and thermal data could provide the basis to diversify the use of leuco dyes as practical phase-change materials and in other applications.
8:00 PM - TP02.03.13
Developing a Novel Platform for Characterizing Thermoelectric Materials for Uncooled Detectors for Land Imaging Applications
Riley Reid1,Emily Barrentine2,Brendan Bramman3,Ari Brown2,Steven Cagiano2,Nicholas Costen2,Vilem Mikula2,Alicia Joseph2
North Carolina State University1,NASA-Goddard Space Flight Center2,University of Waterloo3Show Abstract
Thermal land imaging (imaging at ~8-14 μm optical wavelength) is an essential tool for understanding and managing terrestrial freshwater resources. Current thermal imaging instruments employ low temperature detectors, which require cryocoolers. Consequently, cost-saving reductions in size, weight, and power can be achieved by employing uncooled detectors. One uncooled detector concept, which NASA is pursuing, is a thermopile detector with sub-micron thick doped-Si thermoelectric materials. In order to characterize the thermoelectric properties of the doped silicon, we designed and optimized a novel apparatus. This simple apparatus measures the Seebeck coefficient with thermally isolated stages and LABVIEW automation. We optimized thermal stability using PID tuning and optimized the thermal contact between the thin film samples and stages using electrically conductive springs. Utilizing our apparatus, we measured the Seebeck coefficient of 0.45 micron thick phosphorus-doped single crystal Si samples bonded to alumina substrates. Using these Seebeck coefficient measurements and four-wire electrical resistivity measurements, we determined the relationship between the thermoelectric figure of merit and dopant concentration. These characterization results for doped-Si will guide our thermopile detector design to provide an optimal and competitive detector alternative for future thermal imaging instruments.
8:00 PM - TP02.03.14
Effect of Annealing Temperature and Oxygen Pressure on TiO2 Films Grown on c-Cut Sapphire Substrates via Pulsed Laser Deposition
Alexandra Gordienko1,Anthony Kaye1,2
Texas Tech University1,United States Air Force Nuclear Weapons Center2Show Abstract
Titanium dioxide (hereafter, titania or TiO2) is a well-studied material, but despite of its 100 year history we still don't know everything about this material. It used to be thought that only one of the tetragonal phases of titania - rutile - can be grown on sapphire substrates. That is the reason why a comprehensive study of annealing effects on both phases of titania on c-cut sapphire doesn't exist. In previous works, we developed two pulsed-laser deposition protocols to grow both pure rutile and pure anatase films on this substrate, these protocols are used as the basis of this study.
Titania has a number of properties that make it useful for a wide variety of applications; these include using titania as the basis for energy efficient solar cells, as photocatalytic materials to clean air and water, for self-cleaning coatings, as components of various sensor devices, and as a gate dielectric in MOSFET technologies. Further, because it is a wide bandgap semiconductor, titanium dioxide is becoming increasingly important for many next-generation modern optical and electronics applications, such as transparent electronics systems, transparent thin-film transistors, and see-through active matrix displays. The success of each of these applications depends critically upon the particular crystallographic state (anatase, rutile, or brookite) of the titania being utilized. This is why the annealing effects on the resulting phase of this material can be very important.
Titania thin films were grown via pulsed-laser deposition technique on c-cut sapphire substrates using two pre-determined recipes: one leading to creating pure rutile, and one creating pure anatase films.
Each of the resulting films was post-annealed in a vacuum furnace at different temperatures in 200 to 900 °C in 100 degree increments and at different oxigen pressures (5, 35 and 50 mTorr). The phase of the resulting films was later determined using x-ray diffractometry. Phase content of the films was later analyzed based on the fraction of each phase in overall peak intensity. The quality of each film was was studied using atomic force microscopy.
8:00 PM - TP02.03.15
3D Printed Polypropylene Nanocomposites for Thermal and Electrical Conductivity Applications
Vedant Singh2,Yuval Shmueli1,Daniel Chao3,Ahmed Shata1,Mustafa Zaidi1,Miriam Rafailovich1
Stony Brook University1,The Wheatley School2,Hunter College High School3Show Abstract
Polypropylene (PP) is a common polymer being used in many products in all industrial fields. However, due to its relatively high crystallinity percentages it has difficulties in being produced in the emarging plastics production technology – 3D printing. In this work we show how crystallinity in the printed structure can be advantage due to its orientation that has great potential for conductance applications and also can increase the mechanical properties. We also show how incorporation of thermal conductive nano-fillers as Graphene nano platelets (GNPs) and hexagonal Boron Nitride (hBN) at 0, 5 and 10 wt% combined with the polymer orientation can lead to optimal thermal and electrical conductivity properties of the printed products. We modified the Gcode input to the printer and studied the printing process in order to study the printing conditions for optimal interfilaments fusion and printed product properties.
We used high resolution infra-red thermal camera to measure the thermal conductivity of the printed structure. We also used high voltage resistivity meter to measure the electrical properties. In addition, we used small angle X-ray scattering (SAXS) microbeam to study the macrostructure in the printed structure as function of the radial position from the filaments “skin” and interface to the “core” of the filaments. Our results show the significant improvement to the conductivity properties when the nano-fillers are being introduced to the matrix and in particular, the graphene nano platelets.
We Acknowledge support from the National Science Foundation (Inspire Award No. 1344267) and The Morin Foundation Trust.
8:00 PM - TP02.03.16
Evaluating the Coefficient of Thermal Expansion at Elevated Temperatures through Nanoindentation
Kurt Johanns1,Samuel Bacon1,Phil Webb1,Rich Anthony1,Warren Oliver1
The characteristics of thermal expansion for materials in low volumes is vital to effective manufacturing and service life. High temperature Nanoindentation is seen as a path to effectively evaluate the properties of the thermal expansion in significantly smaller volumes then what is conventionally measured by a thermomechanical analyzer. A series of experiments were run to explore the technique using coated and uncoated samples using molybdenum, aluminum and nickel plated copper to evaluate the potential for the technique to measure material expansion on the nanometer scale. A nanoindenter is found to be able to be able to replicate measurement on bulk materials and is found to be able to provide insight into underlying mechanisms in layered materials expansion.
8:00 PM - TP02.03.17
High IR Transparency of Ultra-Thin Drawn UHMWPE/LDPE and UHMWPE/MDPE Blended Films via Solvent Casting
Yassine Ait-El-Aoud1,Seong Don Hong1,Richard Pang1,Svetlana Boriskina2,Michael Okamoto1,Alkim Akyurtlu3,Richard Osgood1
Natick Soldier Research, Development and Engineering Ctr.1,Massachusetts Institute of Technology2,University of Massachusetts Lowell3Show Abstract
Polyethylene (PE) is well known polymer and has an extremely large spectrum of applications, depending on the particular molecular weight, chain length, and density. The micro and nano-structure polyethylene fibers in arrays have recently attracted great attention mainly in textile fiber industry for wearable personal thermal management. Lately, researchers have shown theoretically  and experimentally  that a particular type of polyethylene, UHMWPE and Nanoporous respectively, is transparent to long wave-infrared body radiation but opaque to visible light. This new passive generation of fabrics could lead to a possible wearable technologies that release heat in hot climates. UHMWPE is a type of polyethylene with extremely long molecular chains that are highly entangled and resulting in a high viscosity after melting. Therefore, UHMWPE raw materials need to be adjusted to meet the melt-spinning processing requirements. It has been shown that the processibilty and flowability of UHMWPE could be improved by 1) adding nanocomposites and/or 2) blending at certain mass ratio with low-density polyethylene (LDPE) or medium density polyethylene (MDPE). Yet, the melt-spinning of ultra-thin drawn UHMWPE/LDPE and UHMWPE/MDPE blended fibers which is our main focus aim remains a challenge whereas the blended films are feasible.
In this study, we have firstly investigated the optical properties of highly oriented ultra-thin drawn UHMWPE/LDPE and UHMWPE/MDPE blended films in the infrared wavelength range (7mm-14mm) via solvent casting. The blended films were drawn at various draw ratio from 5 times to 100 times at 130 °C. Preliminary results showed that highly transparent films with a total transmittance surpassing 95% were obtained by a mass ratio of 8:2 w/w % at draw ratio of 60 times with high crystallinity. The solvent-cast blend films were prepared by pre-mixing polymer powders then adding the mixed powders into decalin solvent in a silicone oil bath. Gradually, the temperature of the oil was increased to 150 °C in three stages within 3 hrs and was stable within ± 0.5°C precision. Secondly, we have been working on developing a thermal model of blended fibers that predict the heat transfer. This thermal model takes into consideration all possible modes of non-radiative heat transfer (convection + conduction) and radiative interaction (total reflection +total transmission +absorption) between skin-fabric and fabric-environment. The temperature cross the fabric is assumed to be uniform and the ambient temperature is approximated large relative to the fabric surface. The air gap between the skin and the fabric is taken sufficiently small.
 Svetlana V. Boriskina et. al "Nanoporous fabrics could keep you cool" Science, Vol. 353, issue 6303, pp. 986-987
 Yi Cui et. al, "Radiative human body cooling by nanoporous polyethylene textile " Science, vol. 353 issue 6303, pp. 1019-1023, September 2016
8:00 PM - TP02.03.18
Fabrication of Shape Memory Polymer Composites Using MWNT and Their Applications to Deployable Antennas
Yongsan An1,2,Yong-min Kim1,2,Yeontae Kim3,Jong Kyoo Park3,Woong-Ryeol Yu1,2
Seoul National University1,Research Institute of Advanced Materials2,Agency for Defense Development3Show Abstract
Deployable antennas have an advantage of good transportability due to their small volume when folded. A space vehicle is launched with folded antenna, which will conduct assigned jobs after unfolded in space. Existing deployable antennas have some drawbacks such as heavy weight and small deformability. Shape memory polymer (SMP), a smart material which can recover the original shape from temporary deformation by external stimulus (e.g., temperature), can be used to overcome these disadvantages. Deployable antennas made up of SMPs have excellent properties such as lightweight, large deformability, good processability, and self-transformation capability without any power devices. However, they are not proper for aerospace application due to limited recovery force and speed caused by low stresses at rubbery states and low thermal conductivity. To enhance the mechanical and thermal properties of SMPs, the shape memory polymer composites (SMPCs) were prepared using surface-modified multi-walled carbon nanotubes (MWNTs) and an epoxy-type of SMP matrix. Raman spectroscopy was used to investigate the increased disorders in the surface of MWNTs after functionalization, which was verified by the XPS analysis. The thermal conductivity of the SMPC was measured by laser flash method. The functional groups in the surface of MWNTs formed covalent bonds with the polymer matrix so that the thermal interfacial resistance of SMPC was reduced, resulting in higher thermal conductivity. Then, the thermomechanical and the shape memory properties of SMPCs were characterized. Finally, a miniature of SMPC antenna (reflector) was fabricated and its deployment test was quantitatively characterized. Improved modulus at the rubbery state and increased thermal conductivity resulted in the high recovery force and speed.
Feng Yi, National Institute of Standards and Technology
Leslie Allen, University of Illinois at Urbana
Martin Kuball, University of Bristol
Sindee Simon, Texas Tech University
National Institute of Standards and Technology
University of Illinois at Urbana-Champaign (Coordinated Science Lab and Material Science & Engineering)
TP02.04: Thermal Properties of Glasses I
Tuesday AM, November 27, 2018
Sheraton, 3rd Floor, Fairfax AB
8:45 AM - TP02.04.01
Kinetics of Stabilization, Polyamorphism and Nanocrystallization in Glasses
John Perepezko1,Meng Gao1,Wei Tang1
University of Wisconsin-Madison1Show Abstract
Thermal analysis and calorimetry have been proven to be of great value in the examination and determination of phase equilibria and thermodynamic properties. For the most part, due to the requirement to establish well defined conditions for measurement and the limitations from equipment design, the applications have been focused on stable equilibria and phases. With the advent of chip calorimetry and Flash DSC (FDSC) which offer unprecedented high programmed heating and cooling rates some of these limitations are removed so that a more extensive examination of phase reactions with rapid kinetics and metastable equilibria is now possible. With this capability it is now possible to explore ranges of alloy metastability and to examine rapid kinetic reactions such as melting and the competition between crystallization and glass formation. These capabilities are demonstrated for the analysis of the glass-to-liquid transition and crystallization of ultrastable glasses and the investigation of vitrification in difficult glass forming metallic alloy and organic liquids. With the expanded heating rate range (up to 40,000 K/s) in FDSC the separation of overlapping glass transition and crystallization signals is possible and has been applied to develop a new method to measure the delay time for nucleation in amorphous Al alloys. Similarly, the expanded cooling rate range (up to 10,000 K/s) in FDSC has allowed for the observation of glass formation and polyamorphism in D-mannitol and the measurement of the complete Time-Temperature-Transformation (TTT) kinetics in metallic glass alloys. These areas offer many opportunities for the application of FSC that can be used to expand the accessible temperature range for the study of the kinetics and thermodynamics of phase transformation and crystallization reactions.
9:15 AM -
9:15 AM - TP02.04.03
In Situ Nanocalorimetry of Thin-Film Stable Glasses
Javier Rodriguez-Viejo1,Aitor Lopeandía1,Marta Gonzalez-Silveira1,Joan Ràfols-Ribé1,Ana Vila1,Llibertat Abad2
Universitat Autònoma de Barcelona1,IMB-CNM-CSIC2Show Abstract
Highly stable glasses prepared by vapour deposition at deposition temperatures around 0.85 of their glass transition temperature exhibit higher density, kinetic and thermodynamic stability with respect to their glassy counterparts obtained directly from the liquid . In these vapor-deposited glasses molecular packing is so tight that the transformation into the supercooled liquid proceeds in time scales much longer than the alpha relaxation time and occurs, for sufficiently thin films, through an heterogenous mechanism starting at the free surface [2-4]. In-situ membrane-based nanocalorimetry is an ideal tool to explore the thermodynamic properties of the glass and its transformation into the supercooled liquid during temperature upscans . By using appropriate capping layers the front mechanism can be suppressed and stable glasses without free surfaces transform through a ‘nucleation and growth’ like process. The transformed fraction follows a sigmoidal shape and can be explained using the KJMAE model, initially derived for crystallization studies. The isothermal kinetic stability increases by a factor of 50 with respect to the uncapped stable glass. We also identify, both in thin films and bulk materials, the existence of a rejuvenation process that is compatible with a cooperative mechanism.
 C. Rodríguez-Tinoco, J. Ràfols-Ribé, M. González-Silveira, J. Rodríguez-Viejo, Evaluation of Growth Front Velocity in Ultrastable Glasses of Indomethacin over a Wide Temperature Interval, J. Phys. Chem. B 118(36), 10795–801, (2015).
 K. Kearns, M. Ediger, H. Huth. C. Schick, One Micrometer Length Scale Controls Kinetic Stability of Low-Energy Glasses, J. Phys. Chem. Lett., 1, 388-392, (2010).
 C.Rodríguez-Tinoco, M.Gonzalez-Silveira, J.Ràfols-Ribé, A.F. Lopeandía and J.Rodríguez-Viejo Transformation kinetics of vapor-deposited thin film organic glasses: Role of stability and molecular packing anisotropy, Phys. Chem. Chem. Phys., 17, 31195-31201 (2015).
 J. Ràfols, C. Rodriguez-Tinoco, M.Gonzalez-Silveira, J. Rodriguez-Viejo, Phys. Chem. Chem. Phys. 19, 11089-11097 (2017).
 J. Rodríguez-Viejo and A. F. Lopeandía. Quasi-adiabatic, membrane-based, highly sensitive fast scanning nanocalorimetry (Book: Fast Scanning Calorimetry, Eds. V. B. F. Mathot and C. Schick). Springer International Publishing, Switzerland, 2016 (ISBN-13: 9783319313276).
10:15 AM - TP02.04.04
Differential Nanocalorimetry and Combinatorial Electrical Resistance Sensors for Analysis of Phase Transformation of Shape Memory Alloys
Juanjuan Zheng1,2,Joost Vlassak1,Yucong Miao1
Harvard University1,Huazhong University of Science & Technology2Show Abstract
Shape memory alloy (SMA) thin films are candidates for the development of micro-actuators. Since the characterization of phase transformations in thin-film samples requires highly sensitive measurement techniques, designing SMAs with optimized composition and heat treatments is challenging. In this study, two recently developed measurement techniques – differential nanocalorimetry and electrical resistance sensors – are used to study high-temperature SMAs. The phase transformations in CuZr thin films are investigated using a differential nanocalorimetry technique with sensitivity as small as 12 pJ/K. We use a general thermal analysis method that allows determination of the heat capacity and enthalpy of transformation of a sample when there is a significant difference in the heat capacities between sample and reference. In addition, we have developed combinatorial sensors that are capable of mapping the resistance of thin-film samples as a function of temperature and composition. The sensors have excellent temperature uniformity, and they are both inexpensive and easy to fabricate. We use the sensors to evaluate the phase transformation behavior of sputter-deposited NiTiFe SMA thin films over a range of compositions. Both the crystallization of the amorphous as-deposited samples and the martensitic transformations in the crystallized samples are readily detected using the resistance sensors. The results show a strong dependence of the phase transformation path and transformation temperatures on composition and heat treatment.
10:30 AM -
11:00 AM - TP02.04.06
Phase Transformation in Nano-Structured Materials Measured by Fast Differential Scanning Calorimetry
Mettler Toledo GmbH1Show Abstract
Fast differential scanning calorimetry (FDSC) is a non-adiabatically chip calorimetry technique. The commercial available Flash DSC 2+ enables typical heating and cooling rates in the order of 40,000 K/s in a temperature range between -100 °C up to 1000 °C.
This technique is used to study the formation of differently structured glasses and non-isothermal nucleating processes in bulk metallic glass alloys. Depending on the thermal history and the heating conditions monotropic polymorphic phases can be formed which can be transformed into the more stable phase on different pathways. Furthermore, we discuss a method to distinguish between heterogeneous and homogeneous nucleation processes.
11:30 AM - TP02.04.07
Conjugated Polyelectrolytes are Feeling the Heat—A Ratiometric Nanothermometer for Solution, Hydrogels and Thin Polymer Films
American University of Beirut1Show Abstract
Temperature is a fundamental variable that controls and drives many chemical, biological and physical processes. Nowadays, there is a tremendous drive to explore and understand processes at the nanoscale level in many fields of science and technology. We report a self-referencing ratiometric nanothermometer based on short conjugated polyelectrolytes (CPEs). The probe is prepared by complexing a phenylene-based polymer with polyvinylpyrrolidone (PVP), an amphiphilic macromolecule that destabilizes the CPE π–π stacking. This makes it possible to shift the equilibrium between the less emissive aggregated state of the CPE (520 nm) and its more emissive single chains (450 nm) within a useful temperature range (15.0–70.0 °C). The probe is used as a noninvasive fluorescent method for mapping thermal fluctuations in solution, hydrogel matrices and thin film polymers using an unmodified commercially available digital single-lens reflex camera (DSLR). We are currenlty exploring thermal processes in microwell structures. The reported temperature sensor has the potential to provide a wealth of information when thermal mapping is correlated with chemical or physical processes.
TP02.05: Thermal Properties of Glasses II
Tuesday PM, November 27, 2018
Sheraton, 3rd Floor, Fairfax AB
1:30 PM - TP02.05.01
Nano-Scale Dynamic Measurements—Flash DSC and Nanobuble Inflation of Ultra-Stable Amorphous Fluoropolymers
Gregory McKenna1,Heedong Yoon1
Texas Tech University1Show Abstract
The advent of novel experimental techniques that make it possible to work with nanogram quantities of material has revolutionized the study of nanoconfined materials. Furthermore, the relevant techniques have also made it possible to investigate novel materials that are only made in extremely small quantities. It is this latter case that we address here. We have succeeded in making and characterizing ultra-stable amorphous fluorocarbon films made by vacuum pyrolysis deposition (VPD). The ultra-stable amorphous fluorocarbon is very deep in the energy landscape or deep glassy section of the “unexplored region” of glasses between the a very low fictive temperature Tf and the glass temperature Tg. By combining rapid chip scanning calorimetry (Flash DSC) with the Texas Tech nanobubble inflation method we not only determine that the deposition conditions lead to a value of Tf that is very near to the Kauzmann temperature TK, but we are also able to measure the viscoelastic response in the temperature regime encompassing TK to slightly above Tg and determine the temperature dependence of the dynamics in this regime. The question ultimately addressed is whether or not the relaxation time (or viscosity) diverges at a finite temperature above absolute zero and near to TK as anticipated in theories in which an ideal glass transition is postulated. The measurements near to and above Tf give upper bounds to the equilibrium relaxation times because in the regime where T>Tf the material has a lower specific volume and lower enthalpy than the equilibrium glassy state. Furthermore, because the Tf is approximately equal to TK, which is 56 K below the Tg in this case, the range of measurements is greater than previously achieved using a 20 million year old amber material. For the amber the glass had a fictive temperature some 43.6 K below Tg. Our results confirm the amber results and are consistent with the idea that the observed Vogel-Fulcher behavior of glass-forming liquids seen above the Tg does not persist into the deep glassy state where T>Tf. Rather the response deviates from the super-Arrhenius behavior of the Vogel-Fulcher function and tends towards an Arrhenius-like behavior, albeit with very high apparent activation energy. These results challenge theories that demand divergence of the relaxation times or viscosities at a finite temperature as well as the idea of an ideal glass transition. The studies were only possible because of our ability to make dynamic, both calorimetric and viscoelastic, measurements on nano- to micro-gram quantities of material.
2:00 PM - TP02.05.02
Profiles in Local Glass Transition Temperature Near and Across Polymer Interfaces
Emory University1Show Abstract
Local thermal analysis using fluorescence has made it possible to map out the profile in local glass transition temperature Tg(z) as a function of position z across a glassy-rubbery polymer-polymer interface. Starting with the weakly immiscible system of polystyrene (PS) and poly(n-butyl methacrylate) (PnBMA) whose bulk Tg values differ by 80 K, we observed a broad and asymmetric dynamical profile in Tg(z) spanning 350-400 nm from one bulk Tg value to another [J. Chem. Phys. 2015, 143, 111101]. We have since observed similar behavior in a number of weakly immiscible systems, consistently showing a longer-ranged Tg(z) perturbation for a lower Tg polymer next to a hard interface than a higher Tg polymer next to a soft interface [J. Chem. Phys. 2017, 146, 203307]. More recently we have explored this difference of hard vs. soft neighboring domain by investigating the Tg(z) profile in PS next to polydimethylsiloxane (PDMS) with varying crosslink density to systematically change the modulus of the neighboring domain without also changing the chemistry of the interface. We observe that the local Tg(z) in PS at a distance of z = 50 nm away from the PS/PDMS interface can vary by 45 K when the PDMS modulus changes from ~1 to 3 MPa, supporting theoretical predictions that modulus is a controlling variable. Interestingly, the length scale z ≈ 70-90 nm at which bulk Tg(z) of PS is recovered for this more strongly immiscible system is significantly shorter than what would be expected (z ≈ 225-250 nm) for this soft neighboring domain based on our previous results. Our studies have also discovered that this strong coupling of the dynamics across dissimilar polymer-polymer interfaces only occurs if the interface has been well formed and annealed to equilibrium suggesting that some aspect during polymer interface formation (broadening of interface, chain interpenetration, or interfacial roughening) may be significant in controlling the observed behavior. Efforts to separate these different factors have led us to investigate rough interfaces and substrates with end-tethered chains finding that low grafting densities, coinciding with the “mushroom-to-brush” crossover regime, result in large increases in local Tg, with Tg(z) profiles consistent with a hard polymer interface [ACS Macro Letters 2018, 7, 269-274].
2:15 PM - TP02.05.03
Cooperativity Length in a Glass-Forming Liquid Determined by a Combination of Calorimetric Methods and Neutron Spin Echo Spectroscopy
Reiner Zorn1,Yeong-Zen Chua2,Christoph Schick2,Jürn Schmelzer2,Olaf Holderer1
Forschungszentrum Jülich GmbH1,University of Rostock2Show Abstract
Recent advances in AC calorimetry and in quasielastic neutron scattering (QENS) by neutron spin echo (NSE) make an experiment possible with the aim of determining the cooperativity length ξ in glass forming materials proposed more than a decade ago by E. Donth. The basic idea of this experiment is to assign a length scale to the AC-calorimetric relaxation time using the spatial resolution of QENS. By comparing the resulting ξ to the value expected from thermodynamic formulae it is possible to decide whether temperature fluctuations have to be taken into account in glass physics.
The main challenge is to find a range of relaxation times that is accessible by both methods. The use of laser modulation extends the dynamical range in AC calorimetry close to 1 MHz. On the other side, NSE spectroscopy nowadays can access relaxation times up to 1 µs. In practice, both limits cannot be attained completely for a given material. In particular, NSE is further limited by the fact that incoherent scattering is required for this type of study.
Although, for these reasons, the dynamic gap could not be closed completely, we can present first results on propylene glycol. The results indicate a better agreement with a thermodynamic calculation involving temperature fluctuations.
2:30 PM - TP02.05.04
Tg and Structural Recovery of Nanoconfined Polystyrene Using Nanocalorimetry
Texas Tech University1Show Abstract
The behavior of glass-forming materials confined at the nanoscale has been of considerable interest over the past two decades with conflicting results sparking debate. Here, I will discuss recent work from my laboratory focusing on the glass transition and associated structural relaxation kinetics of nanoconfined polystyrene using the Mettler Toledo Flash differential scanning calorimeter (DSC). The advantages of the Flash DSC include sufficient sensitivity to measure enthalpy recovery for a single 20 nm-thick film, as well as extension of the measurements to aging times as short as 0.01 s and to aging temperatures as high as 15 K above nominal Tg since high fictive-temperature glass can be created by the fast cooling rates (1000 K/s). Confinement geometries studied include ultrathin films, supported rods, and stacked rods. The Tg depression of thin films is found to be a function of cooling rate, decreasing with increasing cooling rate; whereas, at the highest cooling rates, Tg is the same as the bulk within the error of the measurements. Results for rods also depend on cooling rate, but with supported rods showing elevated Tgs relative to the bulk. Structural recovery is performed as a function of aging time and temperature, and the evolution of the fictive temperature is followed. The aging behavior and relaxation time-temperature map for single ultrathin films will be compared to those for bulk material, as well as to those for nanoconfined rods and stacked samples. The results will also be discussed in the context of current controversies in the field.
2:45 PM - TP02.05.05
Thermal Analysis of Liquid Coatings Using a Unique DMA Method
Xinzhu Gu1,Ed Millero1,Christina Puhnaty1,Qin Li1,Claire Parasida1
PPG Industries, Inc. 1Show Abstract
Dynamic mechanical analysis (DMA) is a highly sensitive thermal mechanical analysis technique for studying the viscoelastic behavior of polymers. It provides insight into the relationship between molecular structure and mechanical properties of polymers, therefore it is a useful tool to monitor vitrification, gelation, curing and decomposition of thermoset polymers. Coatings, in their liquid form, are not suitable for direct DMA testing. Solid supporting substrates, mainly wood and glass fiber, have been used for liquid resins to obtain solid specimens for DMA testing. Specifically, liquid resins were applied on the surface of a supporting substrate to form a sandwich structure then is subjected to DMA testing mainly in three-point bending mode. However, these substrates are not suitable for studying thin coatings due to the large stiffness differences between the substrate and coating. In this study, the liquid polymer coatings were applied to a soft absorbent substrate (i.e. Kimwipe®). The coated Kimwipe® was then used to examine cure properties and glass transition temperatures (Tg) via DMA in tension mode.
The first part of this study investigated the curing behavior of the liquid coatings using a Kimwipe® as the substrate. Before the curing reaction occurred, as temperature increased and liquid carrier evaporated from the coating composition, the modulus of elasticity gradually increased. As temperature kept increasing, rapid increase of the stiffness of polymer was observed, attributed to cross-linking reaction. This change was reflected by a change in the slope of the storage modulus as function of temperature. The inflection point occurring at a specific temperature on DMA curve suggested the onset of curing behaviors. Moreover, degrees of cure were calculated from the modulus vs. temperature curve.
In the second part of this study the dynamic mechanical properties and Tg of the solid coatings obtained from previous tests were investigated and compared with free-standing films. The Tg of coatings and free films were found to be very comparable, while the coatings showed higher storage modulus than free films, given the storage modulus of the substrate.
In summary, the Kimwipe® was proven to be a suitable substrate for the preparation of DMA testing specimens to predict the curing behavior and Tg of liquid coating for its stability during the temperature span. This technique will help understand thermal properties of liquid samples when convectional DSC technique and fabrication of free films are challenging.
TP02.06: Scanning Thermal Microscopy
Tuesday PM, November 27, 2018
Sheraton, 3rd Floor, Fairfax AB
3:30 PM - TP02.06.01
Nanoscale AFM Probes Enable Thermal Conductivity and Chemical Composition Imaging at the Nanoscale
Andrea Centrone1,Georg Ramer1,Vladimir Aksyuk1
National Institute of Standards and Technology1Show Abstract
Atomic force microscopy (AFM) provides thermal, chemical, mechanical etc., properties, at the nanoscale. For example, photothermal induced resonance (PTIR) combines AFM with IR (or visible) spectroscopy. In PTIR, the absorption of a laser pulse induces a rapid thermal expansion of the sample. Conventional cantilevers are too slow to track the sample thermal expansion dynamics; however, the fast sample expansion kicks the cantilever in oscillation (like a struck tuning fork), with amplitude proportional to the absorbed energy.
To capture the sample thermalization dynamic, we introduced the Scanning Thermal InfraRed Microscopy (STIRM) technique. STIRM leverages nanofabricated temperature sensitive AFM probes to measure the temperature raise in the sample due to light absorption. The STIRM signal amplitude is proportional to the absorbed energy, yielding the local chemical composition; while the STIRM signal evolution can provide the sample thermal conductivity at the nanoscale (if the sample thermalization is slower than the probe).
Here we revolutionize AFM (and PTIR) signal transduction by integrating cavity-optomechanics for sensing the motion of fast, nanosized/picogram scale AFM probes with unprecedented precision and bandwidth, thereby breaking the trade-off between AFM measurement precision and ability to capture transient events. Applied to PTIR/STIRM, the probe near-field ultralow detection noise and wide bandwidth improves the time resolution (10 ns, x1500), signal-to-noise ratio (50 x) and throughput (x2500). Remarkably, this synergy enables a new PTIR measurement modality: capturing the previously inaccessible fast thermal-expansion response of the sample to nanosecond laser pulses, thus allowing concurrent measurement of the chemical composition and thermal conductivity, at the nanoscale.
We validate these new capabilities using polymer films and measure the intrinsic thermal conductivity (η) of metal-organic framework (MOF) individual microcrystals, a property not measurable by conventional techniques. MOFs are a class of nanoporous materials promising for catalysis, gas storage, sensing and thermoelectric applications where accurate knowledge of η is critically important. Additionally, the improved sensitivity enables measurement of nanoscale IR spectra of monolayer this sample with high signal to noise ratio (≈ 170).
Finally, I will discuss our efforts to further increase the PTIR throughput by 200-fold, i.e. 500000x with respect to conventional measurements and to conduct measurements in water.
We believe that cavity-optomechanics based probes are broadly-applicable and will benefit a wide range of AFM-based dynamic observations in nanoscience and biology.
 Centrone, A. Annu. Rev. Anal. Chem. 2015, 8, 101-126
 Katzenmeyer, A.M. et al. Nanoscale 2015, 7, 17637-17641
 Chae, J. et al. Nano Lett. 2017, 17, 5587-5594
4:00 PM - TP02.06.02
Influence of Temperature on Microstructure and Mechanical Properties of Polymer Composites
Bede Pittenger1,Sergey Osechinskiy1,Steven Ulrich1,Judy Mosley1,Sophie Loire1,Shuiqing Hu1,Thomas Mueller1
The relationship between the microstructure and mechanical properties of microscopic domains within polymer composites is important due to their influence on macroscopic material performance and function. Mechanical properties of polymers are time dependent, so a full understanding requires measurements over a range of frequencies and temperatures. Ideally, one would like to observe the mechanical behavior of these domains while they pass through their glass transitions in order to better understand the influence of size effects and confinement.
Atomic Force Microscopy (AFM) has the nanometer level resolution and sensitivity needed to investigate these samples, but accurate comparisons with established rheological measurements have proven to be more elusive. Resonant methods like TappingMode and contact resonance provide mechanical property maps at discrete frequencies that are many orders of magnitude higher than bulk measurements. Non-resonant methods like force spectroscopy and PeakForce Tapping provide a better match in frequency, but face challenges in calculating intrinsic mechanical properties like loss tangent and storage modulus.
Recently, new AFM modes, improved modeling, better calibration, and more optimal probe design have become available, expanding the possibilities for quantifying mechanical properties at the nanoscale. This presentation will demonstrate the use of this new capability in examining microscopic domains and interphase regions within a polymer composite over a wide range of frequencies and temperatures.
 O. Sahin, C. Quate, O. Solgaard, and A. Atalar, Phys. Rev. B, 2004, 69, 1.
 U. Rabe, S. Amelio, E. Kester, V. Scherer, S. Hirsekorn, and W. Arnold, Ultrasonics,2000, 38, 430.
 A. Yango, J. Schäpe, C. Rianna, H. Doschke, and M. Radmacher, Soft Matter, 2016, 12, 8297.
 T. J. Young, M. A. Monclus, T. L. Burnett, W. R. Broughton, S. L. Ogin, and P. A. Smith, Meas. Sci. Technol., 2011, 22, 125703.
 B. Pittenger and D. G. Yablon, Bruker Application Note, 2017, AN149, 1.
4:15 PM - TP02.06.03
Quantitative Thermometric Scanning Thermal Microscopy and Thermomechanical Nanoindentation from Room Temperature to >1,000C
Roger Proksch1,Ami Chand2
Asylum Research1,Applied Nanostructures2Show Abstract
The functionality and performance of polymeric materials is largely determined by a complex interplay of chemical and mechanical properties, often at the nanoscale. In order to understand these complex material systems and further improve them, it is necessary to measure and map them at that same nanoscale. Macroscopic polymer behavior is often characterized with temperature dependent mechanical analysis measurements such as dynamic mechanical analysis (DMA). Previous approaches to making similar measurements on the nanoscale, while having some success at quantifying stress and strain as a function contact area and frequency have relied on indirect measurements of the tip-sample contact temperature. Using a combination of a laser heated tip with a unique, an integrated thermocouple combined with a scriptable DMA interface, we can quantitatively evaluate temperature and frequency dependent polymer properties with sub-100nm resolution. This approach has enabled three key advances we will cover in this presentation:
1. High temperature Scanning Thermal Microscopy. The probes discussed here, coupled with photothermal heating can routinely operate at temperatures in excess of 1,000°C.
2. Localized thermal analysis combined with quantitative nanomechanical imaging. The ability to quantitatively ramp the tip temperature (estimated at rates in excess of 108°C /minute) allow quantitative and highly localized measurements of phase transitions, mechanical and other temperature dependent properties.
3. Fouled tip cleaning. A common problem in AFM, fouling of the tip with material from the sample, can be greatly mitigated with localized heating of the tip. We will demonstrate that repeatable quantitative modulus measurements can be accomplished by cleaning the tip with a simple protocol.
The tip structure of the thermocouple integrated probe has been described elsewhere . During the experiments the tip and the thermocouple materials were found to be stable in the excess of 1000° C, expanding the regime of the DMA of the polymeric material that were not possible with existing technologies.
 Fast, High Resolution, and Wide Modulus Range Nanomechanical Mapping with Bimodal Tapping Mode, Marta Kocun et al. ACS Nano, 2017, 11 (10), pp 10097–10105
 Micromachined Chip Scale Thermal Sensor for Thermal Imaging, Gajendra S. Shekhawat et al. ACS Nano, 2018, 12 (2), pp 1760–1767
4:30 PM - TP02.06.04
Development of a Multimodal Imaging Platform Based on Photoinduced Thermal Desorption and Analysis by Atmospheric Pressure Chemical Ionization Mass Spectrometry
Olga Ovchinnikova1,Matthias Lorenz1,Stephen Jesse1,Mario Viani2,Aleksander Labuda2,Roger Proksch2
Oak Ridge National Laboratory1,Asylum Research2Show Abstract
The key to advancing materials is to understand and control their structure and chemistry. Thorough chemical characterization can be challenging since many existing techniques analyze only a few properties of the specimen, thereby requiring multiple measurement platforms to acquire the necessary information. The multimodal combination of atomic force microscopy (AFM) and mass spectrometry (MS) transcends existing analytical capabilities for nanometer scale spatially resolved correlation of the chemical and physical properties of a sample surface. We recently introduced the utilization of a photoinduced cantilever heating technology developed by Oxford Instruments for the localized thermal desorption and analysis and presented a closed cell design for sampling on an Oxford Instruments Cypher ES microscope to interface with a Thermo Orbitrap Velos Pro mass spectrometer using inline atmospheric pressure chemical ionization (APCI). The photoinduced cantilever heating technology works with standard AFM probes that are compatible with advanced AFM modes for the nanomechanical and electromechanical characterization of samples. We previously demonstrated below 500 nm spatial resolution for the spot-sampling by thermal desorption from thin layers and the chemical analysis of small organic molecules in full scan MS mode.
We demonstrate the application of multiple and advanced AFM measurement modes such as AMFM nanomechanical characterization on a single AFM cantilever, combined with photoinduced thermal desorption and analysis by mass spectrometry to link chemical composition with material functionality. We show the chemical analysis by mass spectrometry of gas phase species evolving from polymeric material in contact with a heated AFM probe, spatially resolved with nanometer resolution, and identify small organic molecules and characteristic fragments and pyrolysis products from the polymer. We present results from systematic studies of factors limiting the efficiency of transport and ionization of material evolving from the sample surface, with the objective to enhance the achievable spatial resolution and compound coverage of the multimodal imaging platform. Parameters studied include the timing of the photothermal cantilever heating and analysis by mass spectrometry, transport conditions for the gaseous material from the closed desorption cell to the mass spectrometer, and the operating conditions of the inline ionization stage. Computational fluid dynamics (CFD) simulations were used to study the uptake and transport of material. Experimental studies on prototype cell models prepared by additive manufacturing provide support for the modeling data.
4:45 PM - TP02.06.05
Calibration Techniques for Robust Quantitative Scanning Thermal Microscopy—A Comparison of Strategies and Best Practices
Adam WilsonShow Abstract
As we continue to improve our ability to miniaturize, manipulate and leverage materials and devices down to the nanoscale, the limit to advancement in many fields leveraging nanotechnology is accurate measurement of material properties at these scales. Scanning thermal microscopy (SThM) boasts the best available spatial resolution among thermal metrology techniques, leveraging the nanometer-scale resolution afforded by atomic force microscopy. However, SThM has suffered from a lack of consistent, reliable quantitative usage. This is largely due to tip-sample interaction, with the sample’s topography leading to artifacts in the observed signal. Several recent efforts have attempted to more robustly calibrate the probe-sample thermal interaction and account for topographically-induced artifacts. Among the most commonly used thermal exchange parameter calibration strategies are the implicit (curve fitting) method, the step method, and the intersection method, which each rely on at least two materials as reference samples, while recent advancements include single-sample calibration strategies. However, to date, there has not been a comparative study between calibration methods, or efforts to demonstrate the limits of each technique.
This work compares the performance and suitability of probe-sample thermal exchange calibration strategies, discusses the most frequent failure modes, and offers guidance for best practice in quantitative usage of SThM. As an example of determination of accuracy of calibration and best practices, we demonstrate that under conditions previously published using the intersection technique (klow = 1.1 Wm-1K-1and khigh= 1.5 Wm-1K-1), significant deviation (>50%) in measured sample thermal conductivity is observed when measuring samples with thermal conductivity values larger than those of the reference samples, but we demonstrate that by calibrating with reference samples having a wide range of sample thermal conductivity (klow = 0.5 Wm-1K-1 and khigh = 50 Wm-1K-1), the measured values may be expected to be accurate to within 20% for the entire range. Similar analysis will be performed on data from both previously published studies and new experimental results using the step method, the implicit method, and the novel single-sample calibration strategies to demonstrate which method(s) provide the most accurate values for local thermal conductance measurement and in what ranges and experimental conditions the quantitative accuracy may hold. This work is poised to offer a timely comparison between several emerging and widely used calibration techniques for SThM, and aims to unify efforts for improved accuracy and reliability in future quantitative studies using SThM.
TP02.07: Poster Session II
Tuesday PM, November 27, 2018
Hynes, Level 1, Hall B
8:00 PM - TP02.07.01
Influence of Temperature on the Pop-in Load and Indentation Size Effect of Single Crystal Brittle Material
Janel Chua1,2,Qingsong Tu3,Hao Wang1
National University of Singapore1,DSO National Laboratories2,University of California-Berkeley3Show Abstract
In this work, the indentation size effect (ISE) is studied for temperatures ranging from 300K to 475K using nanoindentation experiments and molecular dynamics simulations. CaF2 single crystals are indented using a high temperature nanoindenter and the pop-in load was observed to decrease with increasing temperature. Increasing the temperature of the material also led to a reduction in the material dependent plasticity length scale defined in the Nix-Gao relation as well as the hardness at infinite depths.
The experiment is supplemented with MD simulations of nanoindentation into a free surface of CaF2. A suitable CaF2 potential for high temperature was first selected via comparisons between simulated and experimental vacancy formation energy as well as melting point temperatures. Changes in dislocation structure with increasing indentation depth were then studied for various temperatures for the (111) planar direction. The study thus provides much insight into the relationship between temperature and dislocation mechanisms during nanoindentation and underscores the effect of temperature on dislocation structure and formation.
8:00 PM - TP02.07.02
Reduction in Thermal Conductivity by Phonon Confinement Effect of In0.53Ga0.47As Nanofilms
Hoon Kim1,Jungwon Kim1,Mehmet Kilic1,Chhatrasal Gayner1,Rachel Koltun2,Hwanjoo Park1,Aloysius Soon1,John Bowers2,Chris Palmstrom2,Woochul Kim1
Yonsei University1,University of California, Santa Barbara2Show Abstract
Reduction in thermal conductivity of the nanostructured materials has been widely known for having the reduced phonon mean free path by its nano-size boundary scattering. At even smaller size, the phonon confinement effect from the decrease of the phonon group velocity can happen in nanostructured materials leading to further reduction in the thermal conductivity. We measured the thermal conductivity of In0.53Ga0.47As nanofilms with various thicknesses from 70 to 10 nm by the T-bridge method, and analyzed it by the Callaway’s thermal conductivity model. It is found that the calculated thermal conductivities of below 20-nm-thick nanofilms based on the bulk In0.53Ga0.47As group velocity cannot accurately predict the measured thermal conductivities. The group velocities of nanofilms are evaluated by the calculation of the phonon dispersion relation, and these show that there is a significant reduction in the group velocity along the decrease in the thickness. According to these reduced group velocities, the re-calculated thermal conductivities of below 20-nm-thick nanofilms are successfully agreed with the measured ones. The phonon confinement effect is found to be another key factor to explain the low thermal conductivities of below 20-nm-thick In0.53Ga0.47As nanofilms.
8:00 PM - TP02.07.03
Extraordinary Electronic Contribution to Thermal Transport in Free-Standing Graphene Nanoribbons with Low-Disorder Edges
Qinyi Li1,Wakana Okita2,Hiroo Suzuki2,Toshiaki Kato2,Toshiro Kaneko2,Yohei Komori1,Tatsuya Ikuta1,Koji Takahashi1
Kyushu University1,Tohoku University2Show Abstract
Previous research on thermal transport in graphene has focused on the lattice contribution while the electronic contribution is regarded as 0.1%~1%. Here, we report experimental evidence of extraordinary electronic contribution to heat conduction in graphene nanoribbons (GNRs) with low-disorder edges. By the electrical self-heating method, the thermal conductivity of a plasma-CVD-grown 43nm-wide suspended GNR with near-zigzag edges was measured to be below 5% of that of large pristine graphene and exhibits a temperature dependence that indicates width confinement. The electronic thermal conductivity, which is converted from the measured electrical conductivity by the Wiedemann-Franz law, reaches as high as ~20% of the total thermal conductivity at 120-360K. This finding is attributed to the different effects of edge scattering on phonons and electrons for the particular edge structure, as well as the cleanness of the as-grown sample. Even the low level of edge disorder in the near-zigzag GNR can lead to strong phonon-edge scattering, but the superior electron transport is preserved, which agrees well with previous simulations. Our work highlights the importance of electronic thermal conductivity in GNRs, and suggests the edge manipulation as a promising way to independently control electron and phonon transport in GNRs for potential thermoelectric applications.
8:00 PM - TP02.07.04
Non-Contact Temperature Difference Measurement of Cleavage Plane Nanogap Electrodes with Large Surface Area
Masaki Shimofuri1,Yoshikazu Hirai1,Toshiyuki Tsuchiya1,Osamu Tabata1
Kyoto University1Show Abstract
Vacuum nanogap electrodes are expected to significantly improve thermal power generation efficiency, which is considered difficult with conventional thermoelectric materials. In order to apply the vacuum nanogap electrodes as a thermal power generation element, the properties of nanogap, especially heat transfer at the nanogap should be investigated because enhancement of the heat transport due to the near-field heat radiation effect cannot be ignored in the vacuum gap of nanometer order. However, the measurement is difficult because it needs high temperature and spatial resolution. In addition, it is difficult to create a spatial temperature difference in a nanometer scale region. Furthermore, it is also challenging to achieve both large area and uniform narrow gap by conventional fabrication methods such as electron beam lithography, metal plating, and focused ion beam processing, where the opposing surfaces of the gap are neither parallel nor flat. Also, the emission area achieved by the aforementioned methods are only of the order of several nm2, which makes these vacuum nanogap electrodes impractical from the viewpoint of the power generation. In this research, we have proposed a method to make nanogap electrodes by exploiting the advantages of interplanar cleaving in single crystal silicon, choosing (111) as cleavage plane. In cleavage fracture, a smooth fracture surface parallel to the crystal plane is exposed, so it is expected that the opposing surface of the obtained nanogap electrodes will become parallel and smooth. We fabricated MEMS devices with silicon-on-insulator wafers with device layer thickness of 5 um, oxide sacrificial layer thickness of 2 um, handle layer thickness of 400 um, device layer surface orientation (110). Silicon beam in the device, oriented in <111> direction was cleaved by applying tensile stress using a micromanipulator. As a result, nanogap electrodes having a parallel and smooth surface area of several tens of um2 were obtained, which makes the cross-sectional area several thousand times larger than conventional nanogap electrodes. Comb drive actuators and a gold wire for joule heating were integrated in the device, and the gap distance control and heating near the nanogap electrodes were carried out. For temperature measurement, mirco-Raman spectroscopy was used. The temperature resolution in our measurement was about 1 K and the spatial resolution was 1 um or less. We were successful to produce and maintain a spatial temperature difference of up to 60 K in a 180 nm size distance. However, in order to evaluate the proximity effect of heat transfer in the vacuum nanogap, higher temperature resolution and accuracy is needed; therefore, we continue to improve the temperature measurement method and device design.
8:00 PM - TP02.07.05
Heat Generation Property of Thick Film Ceramic Heater Consisting of CaCu3Ru4O12
Akihiro Tsuruta1,Toshio Itoh1,Masashi Mikami1,Yoshiaki Kinemuchi1,Ichiro Terasaki2,1,Norimitsu Murayama1,Woosuck Shin1
AIST1,Nagoya University2Show Abstract
We have studied a conducting oxide CaCu3Ru4O12 as an alternative conducting material for Pt in various high temperature operating electrical devices such as solid oxide fuel cells and gas sensors. The resistivity of CaCu3Ru4O12 is lower than 1 mΩcm even at 500°C, and the temperature dependence of resistivity is metallic. In our previous study, we have successfully formed CaCu3Ru4O12 thick film on an alumina substrate by screen printing process, which is one of the practical process, via mixing with CuO as a sintering additive . Then, we have fabricated a SnO2 gas sensor using CuO-mixed CaCu3Ru4O12 thick film as both electrodes and a heater on an alumina substrate (3.0 × 25 × 0.3 mm). In this study, we investigated the heat generation property of the CuO-mixed CaCu3Ru4O12 thick film heater in the sensor in order to evaluate the potential of CaCu3Ru4O12 .
The temperature of the CuO-mixed CaCu3Ru4O12 thick film heater increases at least up to 600°C without any problems such as thermal runaway and hot spots, and the temperature is linearly changed with applied voltage. The heater remains intact after long-term operation at high-temperature and a large temperature change of 500°C within 10 s. We conclude that the CuO-mixed CaCu3Ru4O12 thick film heater is proven to be robust and reliable, and can replace Pt heaters in gas sensor.
 A. Tsuruta et al.: Phys. Status Solidi A 214 (2017) 1600968.
 A. Tsuruta et al.: Materials 11 (2018) 981.
8:00 PM - TP02.07.06
Influence of Heterogeneous Pnictogen-Substitution on Thermal Transport in Skutterudites
Semi Bang1,Georgy Samsonidze2,Boris Kozinsky3,Daehyun Wee1
Ewha Womans University1,Robert Bosch LLC2,Harvard University3Show Abstract
The materials class of skutterudites is considered to be one of the most promising state-of-the-art thermoelectric (TE) materials. The archetypical binary skutterudites, CoSb3 exhibit excellent electrical transport properties, but the thermal conductivities of binary skutterudites are too large for TE applications. On the other hand, the pnictogen-substituted ternary skutterudites (PSTSs), which are modified by heterogeneous pnictogen-substitution with group 14 (Ge, Sn) and group 16 (S, Se, Te) elements, are experimentally observed that there is the significantly lower thermal conductivity of PSTSs than CoSb3. It has been considered as the attractive features to be investigated as potential thermoelectric materials. However, the understanding of the chemical substitution effect on thermal transport in PSTSs is still insufficient.
In this study, we investigate the effect of pnictogen-substitution on thermal transport in order to gain a deeper understanding of transport phenomena in PSTSs by estimation of thermal transport properties with quasi-harmonic (QHA)-based modified Debye-Callaway model. This method is modified in order to consider various scattering mechanisms, including phonon-phonon (ph-ph; normal and Umklapp), phonon-electron (ph-el), and mass fluctuation, since these scattering mechanisms become significant factors on the thermal transport in complex and realistic TE materials. In particular, the phonon scattering rate arising from the ph-el interaction is estimated by a newly developed method in this study. Hence, we also verify the feasibility of this developed computational methodology for thermal transport. Based on our results, we consequently provide certain guidance for the rational design of next-generation TE materials.
8:00 PM - TP02.07.07
Optical Pump Thermoreflectance Imaging of Metal-Polymer Composite Thin Films
Kerry Maize1,2,Jesus Leon Gil1,2,Ali Shakouri1,2
Birck Nanotechnology Center1,Purdue University2Show Abstract
State of the art composite materials often have complex heterogeneous or anisotropic microstructure. Measurement of microscale thermal inhomoegeneity can be helpful in understanding and optimizing performance. In their default configurations well established methods to measure thermal conductivity such as 3-ω, laser flash analysis, and time domain thermoreflectance measure average thermal response over a given sample volume and often information about microscale inhomogeneity is not included in the result. Here we introduce optically pumped thermoreflectance imaging microscopy to inspect microscale nonuniform surface temperature in thin film and bulk materials in response to laser spot heating. Experiment configuration is identical to previous examples of thermoreflectance imaging microscopy, but instead of thermally pumping the sample by an electrical signal the sample is optically pumped by a laser spot focused on the sample surface. The method is capable of rapid, noncontact thermal images of bare target materials without requiring special sample preparation such as fabricated heater lines or transducer layers. Spatial resolution is submicron (diffraction limited). Temperature resolution is 50 milliKelvin. Time resolution is 50 nanoseconds. High magnification images of laser spot heaing are presented for a PDMS polymer matrix embedded with nickel clusters. Typical Ni cluster diameter is 20 microns. Pump excitation of 10 milliwatts using an 825 nm diode laser focused to a one micron spot on the sample surface revealed nonuniform microscale temperature distribution with strong dependence on the proximity of high thermal conductance Ni clusters. Experiments are underway to demonstrate additional applications of optical pumped thermoreflectance imaging, such as separate measurement of in-plane and cross-plane thermal conductivity in anisotropic samples by varying the size of the pump laser spot size.
8:00 PM - TP02.07.08
A Study of Undercooling Behavior of W-Ta Binary Alloys Using High Temperature ESL Equipment
Ilhwan Kim1,Chae Woo Ryu1,Geun Woo Lee2,Eun Soo Park1
Seoul National University1,Korea Research Institute of Standards and Science2Show Abstract
The nickel or cobalt based superalloys which used for high temperature structural materials have the problem that rapidly decrease mechanical properties above 1400 °C. Because nickel and cobalt have melting temperature near 1500 °C, this physical property of superalloys limits the structural application over ultra-high temperature region. To operate as fusion reactor materials or to improve efficiency of turbine engines, development of ultra-high temperature structural new materials has to be required. As alternative materials, ceramic based heat resistant materials are suggested. But these materials have large brittleness that can be easily fractured by applied stress. On the contrary, refractory metal elements which have melting temperature over 2000 °C are ductile comparing to high temperature ceramic materials. And comparing to nickel based superalloys, refractory elements have superior mechanical properties until ultra-high temperature region. It is the reason why there are some researches for using refractory metal alloys as ultra-high temperature structural materials. However, the study of ultra-high temperature property of refractory alloys is limited by melting of crucible, high temperature oxidation and absence of equipment which is able to heat up to ultra-high temperature. Therefore containerless experiment is much required for restraining melting of container and measuring accurate thermal properties. W-Ta binary alloys, which are complete solid solution system, have high melting point above 3000 °C. The high temperature electrostatic levitation (ESL) equipment is suitable for measuring thermal properties of W-Ta binary alloy systems having such a high melting point. As a result, W-Ta alloy in levitated equipment showed deep undercooling over 600 °C. Because there is no contact between sample and crucible, homogeneous solidification behaviour with deep undercooling was observed. The microstructure was different between crucible solidified sample, and levitating solidified sample. Deep undercooling in homogeneous solidification induced fast growth of primary dendrite arms, on the other hand heterogeneous solidification induced thick and short primary dendrite arms. Finally, Microstructure was investigated to figure out solidification behaviour of each condition and to control mechanical and thermal properties of W-Ta alloys. Likewise to previous research, deep undercooling sample had long primary dendrite arms and low secondary dendrite arm spacing, which can induce higher yield strength than heterogeneous solidification sample. Ultimately, because the study of properties near melting temperature of W-Ta alloys is deficient for lack of systematic experiment, this study can be a touchstone to study of measuring property of ultra-high temperature refractory alloys.
8:00 PM - TP02.07.09
The Role of Molecular Chain Length and Side Group Weight on Thermal Transport In Electrospun Vinyl Polymer Nanofibers
Xin Zhang1,Yin Zhang2,Lin Yang1,Qian Zhang1,Akira Ueda3,Matthew Fitzgerald1,Richard Mu4,Deyu Li1,Leon Bellan1
Vanderbilt University1,Southeast University2,Fisk University3,Tennessee State University4Show Abstract
Polymeric materials have found extensive use in a variety of applications due to their facile synthesis and processing, low-cost and tunable and attractive properties. Since a recent studying employing molecular dynamics techniques suggested that a single-chain polyethylene (PE) could possess extremely high thermal conductivity (~350 Wm-1K-1) several research efforts have been devoted to investigating a variety of factors that may result in the enhanced thermal transport in polymer nanofibers. Recent experimental results have demonstrated that the thermal conductivity of an individual ultra-drawn polyethylene nanofiber can achieve ~104 Wm-1K-1, which is three orders of magnitude larger than that of bulk PE. However, the dependence on several critical factors, such as molecular chain length and side group composition, is still not understood.
To explore the influence of molecular chain length, we prepared PE nanofibers with four different molecular weights (Mw) using the electrospinning process. The thermal conductivity of various electrospun PE nanofibers was determined using a well-established thermal bridge device composed of suspended microheaters/thermometers. Our results indicate that nanofibers composed of higher molecular weight polymers exhibit larger thermal conductivity, which is attributed to more efficient energy transport along the polymer chain direction compared to cross chain direction. It is noteworthy that PE fibers with lower Mw (35,000 and 125,000) exhibit monotonically increasing thermal conductivity versus temperature, typical for amorphous materials. However, for higher Mw PE fibers (420,000 and 3,000,000), a peak thermal conductivity appears as temperature increases, which is a signature of phonon Umklapp scattering in crystalline materials.
To investigate the impact of side group composition, we electrospun three types of vinyl polymer nanofibers, namely polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA) and polyvinyl chloride (PVC). These polymers have the same planar-zigzag carbon backbones as PE, but with one or two hydrogen atoms replaced by different heavier side groups (OH, Cl or F) in each monomer unit. In order to examine the role of side groups, we purposely choose the molecular weight of all polymers such that their polymer chain lengths were as close as possible. The measured thermal conductivity of four different types of polymer fibers shows a clear trend indicating κPE > κPVA > κPVDF > κPVC, which implies that thermal conductivity decreases as the side group becomes heavier. Additionally, it is believed that the enhanced thermal conductivity of electrospun nanofibers may correlate with their increases in Young’s modulus. As such, we measured the Young’s modulus of several individual electrospun PVA, PVC and PVDF nanofibers using an atomic force microscope. The measured Young’s modulus of PVA was larger than that of PVC and PVDF, which agrees with the thermal conductivity trend.
8:00 PM - TP02.07.10
Tuning Thermal and Electrical Properties of NiOx Films by UV/O3 Treatment for Resistive Memory Applications
Sanchit Deshmukh1,Raisul Islam1,Christopher Saltonstall2,Eilam Yalon1,Thomas Beechem2,Krishna