Detection and Characterization of Chemicals Present in Tank Waste - Final Report - 09/15/1998 - 09/14/2001

DOE has a strong commitment to the efficient and safe remediation of waste (high level radioactive waste, mixed waste, and hazardous waste) present in underground waste storage tanks. Safety issues arise from the presence of organic chemicals and oxidizers and concerns are raised about the flammability, explosivity, and the possible corrosion of storage tanks due to presence of nitrates and nitrites. Knowledge of the physical parameters and chemical and radioactive composition of waste is necessary for effective and safe tank remediation. New and improved characterization and monitoring of waste present in storage tanks is necessary. The overall goal of this project has been to develop and demonstrate novel multi-parameter micro-electro-mechanical system (MEMS) sensors based on Si and SiNx microcantilever (MC) structures that are robust and can be used to simultaneously detect the presence of target chemicals (analytes) in a mixture, radiation emitted from radioactive materials, an d the heat generated by the absorption of photons of specific wavelength by the target analytes. The mechanisms by which adsorption, photophysical, photothermal processes cause stress in MC surfaces are better understood. Methods of applying a wide variety of chemically selective coatings have been developed specifically for miniaturized MC surfaces, and the response characteristic of the cantilever were shown to be altered dramatically and predictably through incorporation of these phases on the surfaces. By addressing sensitivity and liquid matrix issues, the spectroscopic approach promises to provide an essential element of specificity for integrated sensors. We discovered early in these studies that fundamental limitations exist regarding the degree to which adsorption of analytes on smooth surfaces cause stress and this significantly limits chemi-mechanical response. To circumvent this limitation a concerted effort was made to devise and test ways to nanostructure cantilever surfaces, thereby creating new mechanisms of analyte-induced stress. Substantial improvement in chemi-mechanical response resulted from this work

Hybrid Micro-Electro-Mechanical Systems for Highly Reliable and Selective Characterization of Tank Waste

Our multifaceted research program is aimed at the fundamental and practical development of hybrid micro-electro-mechanical-systems (MEMS) that integrates several elements of chemical selectivity and sensor function. We are developing MEMS sensors that combine chemimechanical transduction, and surface enhanced Raman spectroscopy (SERS) and radiation detection. One of our goals is to develop highly effective methods of immobilizing a wide variety of molecular and ionic recognition phases onto micromechanical surfaces. We have introduced fundamentally new modes of adsorbate-induced surface stress through nano-structuring of microcantilever surfaces; the responsivity for has increased by over two-orders of magnitude over previously existing technological approaches. Noble metal nanostructures similar to those that enhance chemi-mechanical transduction exhibit substantial Raman enhancement factors

Hybrid Micro-Electro-Mechanical Systems for Highly Reliable and Selective Characterization of Tank Waste

The main objective of this research program is to develop robust and reliable micro-electro-mechanical sensing systems, based on microcantilevers (MCs), that can operate in liquid environments with high levels of sensitivity and selectivity. The chemical responses of MCs result from analyte-induced differential stress at the cantilever surfaces. We aim to employ various surface nanostructuring strategies that enhance these stresses and hence the degree of static bending of the cantilevers. Receptor phases as self assembled monolayers (SAMs) and thin films are being synthesized and tested to provide selectivity. Selectivity is chemically enhanced by using different phases on individual MCs in arrays and by adding a spectroscopic component, surface enhanced Raman spectrometry (SERS), in hybrid approaches to sensing. Significant progress was made in tasks that were listed in the work plan for DOE EMSP project ''Hybrid Micro-Electro-Mechanical Systems for Highly Reliable and Selective Characterization of Tank Waste''. Several project areas are listed below and discussed and referenced to our literature on the topics

Strong and Electrically Conductive Graphene-Based Composite Fibers and Laminates

Graphene is an ideal candidate for lightweight, high-strength composite materials given its superior mechanical properties (specific strength of 130 GPa and stiffness of 1 TPa). To date, easily scalable graphene-like materials in a form of separated flakes (exfoliated graphene, graphene oxide, and reduced graphene oxide) have been investigated as candidates for large-scale applications such as material reinforcement. These graphene-like materials do not fully exhibit all the capabilities of graphene in composite materials. In the current study, we show that macro (2 inch × 2 inch) graphene laminates and fibers can be produced using large continuous sheets of single-layer graphene grown by chemical vapor deposition. The resulting composite structures have potential to outperform the current state-of-the-art composite materials in both mechanical properties and electrical conductivities (>8 S/cm with only 0.13% volumetric graphene loading and 5 × 10³ S/cm for pure graphene fibers) with estimated graphene contributions of >10 GPa in strength and 1 TPa in stiffness