Massimiliano Zamengo

Silk fibroin as a water-soluble bio-resist and its thermal properties

Thermal diffusivity of silk fibroin films, α = (1.6 ± 0.24) × 10−7 m2 s−1, was measured by a direct contact method. It was shown to be reduced down to ∼1 × 10−7 m2 s−1 in the crystallized phase, consistent with the multi-domain composition of β-sheet assemblies. Crystalline silk with β-sheets was made by dipping into alcohol and was used as a positive electron beam lithography (EBL) resist. It is shown by direct IR imaging of the 1619 cm−1 amide-I CO spectral signature and 3290 cm−1 amide-A N–H stretching band that an e-beam is responsible for unzipping β-sheets, which subsequently results in exposed areas returning to a water soluble state. This makes it possible to develop a water-based biocompatible silk resist and use it in lithography applications. The general principles of protein crystallization, traceable to spectral changes in IR amide bands of silk, can be used as a guide for the creation of new protein EBL resists and to quantify the electron dose required for solubility. Foam formation and laser treatments of silk can provide new approaches in surface functionalization and fabrication of 3D bio-scaffolds.

Nanostructured Antireflective and Thermoisolative Cicada Wings

Inter-related mechanical, thermal, and optical macroscopic properties of biomaterials are defined at the nanoscale by their constituent structures and patterns, which underpin complex functions of an entire bio-object. Here, the temperature diffusivity of a cicada (Cyclochila australasiae) wing with nanotextured surfaces was measured using two complementary techniques: a direct contact method and IR imaging. The 4-6-μm-thick wing section was shown to have a thermal diffusivity of α⊥ = (0.71 ± 0.15) × 10(-7) m(2)/s, as measured by the contact temperature wave method along the thickness of the wing; it corresponds to the inherent thermal property of the cuticle. The in-plane thermal diffusivity value of the wing was determined by IR imaging and was considerably larger at α∥ = (3.6 ± 0.2) × 10(-7) m(2)/s as a result of heat transport via air. Optical properties of wings covered with nanospikes were numerically simulated using an accurate 3D model of the wing pattern and showed that light is concentrated between spikes where intensity is enhanced by up to 3- to 4-fold. The closely packed pattern of nanospikes reduces the reflectivity of the wing throughout the visible light spectrum and over a wide range of incident angles, hence acting as an antireflection coating.

Black-CuO: surface-enhanced Raman scattering and infrared properties.

Large surface area samples of nanotextured black CuO were prepared by chemical etching of Cu for use in surface-enhanced Raman scattering (SERS). The SERS intensity of a self-assembled monolayer (SAM) of thiophenol was proportional to the thickness of a nanoscale-conformal Au film deposited by magnetron sputtering over the black CuO. A very high SERS yield of ∼10(4) counts per s per mW was observed for the thiophenol SAM on the thickest Au films studied here. Synchrotron X-ray photoelectron spectroscopy was used to confirm that the surface of the chemically etched Cu was covered by high purity CuO. IR spectral characterization of the black CuO showed a close to linear increase in reflectivity from 25 to 100% over the range of 4000-500 cm(-1) wavenumbers (or 2.5-20 μm in wavelength). Sensing applications and thermal effects in SERS are discussed.

Si-based infrared optical filters

Abstract. Pyramidal silicon nanospikes, termed black-Si (b-Si), with controlled height of 0.2 to 1  μm, were fabricated by plasma etching over 3-in wafers and were shown to act as variable density filters in a wide range of the IR spectrum 2.5 to 20  μm, with transmission and its spectral gradient dependent on the height of the spikes. Such variable density IR filters can be utilized for imaging and monitoring applications. Narrow IR notch filters were realized with gold mesh arrays on Si wafers prospective for applications in surface-enhanced IR absorption sensing and “cold materials” for heat radiation into atmospheric IR transmission window. Both types of filters for IR: spectrally variable and notch are made by simple fabrication methods.

Micro-scale thermal imaging of CO2 absorption in the thermochemical energy storage of Li metal oxides at high temperature

Li-Metal oxides (typical example: lithium ortho-silicate Li4SiO4) are regarded as a novel solid carbon dioxide CO2 absorbent accompanied by an exothermic reaction. At temperatures above 700°C the sorbent is regenerated with the release of the captured CO2 in an endothermic reaction. As the reaction equilibrium of this reversible chemical reaction is controllable only by the partial pressure of CO2, the system is regarded as a potential candidate for chemical heat storage at high temperatures. In this study, we applied our recent developed mobile type instrumentation of micro-scale infrared thermal imaging system to observe the heat of chemical reaction of Li4SiO4 and CO2 at temperature higher than 600°C or higher. In order to quantify the micro-scale heat transfer and heat exchange in the chemical reaction, the superimpose signal processing system is setup to determine the precise temperature. Under an ambient flow of carbon dioxide, a powder of Li4SiO4 with a diameter 50 micron started to shine caused by an exothermic chemical reaction heat above 600°C. The phenomena was accelerated with increasing temperature up to 700°C. At the same time, the reaction product lithium carbonate (Li2CO3) started to melt with endothermic phase change above 700°C, and these thermal behaviors were captured by the method of thermal imaging. The direct measurement of multiple thermal phenomena at high temperatures is significant to promote an efficient design of chemical heat storage materials. This is the first observation of the exothermic heat of the reaction of Li4SiO4 and CO2 at around 700°C by the thermal imaging method.

Analysis of CO2 reaction of thermochemical energy storage system at high temperature by superimposed micro-scale thermal imaging method (Conference Presentation)

Thermochemical energy storage (TcES) is one of the solutions that use reversible endothermic and exothermic chemical reactions for heat storage and output, respectively. It has several advantages such as a high thermal storage density, and a constant temperature output owing to chemical equilibrium, etc. Recently, carbonation and decarobonation reaction process in Li metal oxide is proposed for use in thermochemical energy storage (TcES) and chemical heat pump (CHP) systems at around 700 °C with the cyclic reaction durability. This system is unique because there is no reported material that can be used for TcES at around 700 °C, even though this is becoming a very important temperature range for heat utilization in solar thermal power plants, high-temperature gas-cooled reactors, and for hydrogen production by fuel reforming. In this study, the method signal imposing visualized a lithium orthosilicate/carbon dioxide (Li4SiO4/CO2) reaction by absolute temperature image transformed from the decoded imposed analog temperature data. The exothermic carbonation, the endothermic solid-liquid phase change, and the endothermic decarbonation are thermally visualized above 700 °C. The analysis of the reaction surface of the carbonateoxide external shell is to be utilized to quantify the lithium diffusion to further form carbonate.

Superimpose signal processing method for micro-scale thermal imaging of solar salts at high temperature

The global interest in energy applications activates the advanced study about the molten salts in the usage of fluids in the power cycle, such as for transport and heat storage in solar power facilities. However, the basic properties of molten salts show a general scattering in characterization especially in thermal properties. It is suggested that new studies are required on the measurement of thermal properties of solar salts using recent technologies. In this study, micro-scale heat transfer and phase change in molten salts are presented using our originally developed device: the micro-bolometer Infrared focal plane arrays (IR FPA) measuring system is a portable type instrument, which is re-designed to measure the thermal phenomena in high temperature up to 700 °C or higher. The superimpose system is newly setup adjusted to the signal processing in high temperature to realize the quantitative thermal imaging, simultaneously. The portable type apparatus for a quantitative micro-scale thermography using a micro-bolometer has been proposed based on an achromatic lens design to capture a micro-scale image in the long-wave infrared, a video signal superimposing for the real time emissivity correction, and a pseudo acceleration of a timeframe. Combined with the superimpose technique, the micro-scale thermal imaging in high temperature is achieved and the molten flows of the solar salts, sodium nitrate, and potassium nitrate are successfully observed. The solar salt, the mixture of sodium nitrate and potassium nitrate, shows a different shape of exothermic heat front morphology in the lower phase transition (solidification) temperature than the nitrates on cooling. The proposed measuring technique will be utilized to accelerate the screening step to determine the phase diagram and the eutectics of the multiple mixtures of candidate molten salts, which may be used as heat transport medium from the concentrated solar power to a processing plant for thermal energy storage.