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Raman spectroscopy is typically envisioned as an in situ analysis technique. Raman spectra measured remotely (10s of meters) from a planetary lander can be calibrated to spectral radiance and the Raman scattering efficiency can be determined.
A modification to a commercial Fourier Transform (FT) Raman spectrometer is presented for the elimination of thermal backgrounds in the FT Raman spectra. The modification involves the use of a mechanical optical chopper to modulate the continuous wave laser, remote collection of the signal via fiber optics, and connection of a dual-phase digital-signal-processor (DSP) lock-in amplifier between the detector and the spectrometer's collection electronics to demodulate and filter the optical signals. The resulting Modulated Fourier Transform Raman Fiber-Optic Spectrometer is capable of completely eliminating thermal backgrounds at temperatures exceeding 300 C.
The intent of this paper and its companion paper is to pull together the essential information required for the traditional Raman lidar data analysis to be performed. As a part of this, complications such as the temperature dependence of the water vapor signal is evaluated through numerical simulation. A new form of the lidar equation is presented that accounts for the temperature dependence of Raman scattering. Also the calculation of atmospheric transmission is examined carefully. Several photon correction techniques are considered as is the influence of multiple scattering on the measurement of aerosol extinction using the Raman lidar technique.
A broad overview of the research that is taking place in the Code 924 Raman Lidar group will be presented. The measurement capabilities of two instruments, the Scanning Raman Lidar (SRL) and the Raman Airborne Spectroscopic Lidar (RASL), will be discussed. Case studies to be presented include: 1) high resolution measurements of water vapor during a boundary layer bore wave event; 2) a study of the influence of thin cirrus clouds on satellite retrievals of water vapor; 3) the retrieval of warm cloud properties such as droplet radius and number density; and 4) remote aerosol characterization using multiwavelength lidar and others.
Ocean Raman scattering significantly contributes to the filling-in of solar Fraunhofer lines measured by satellite backscatter ultraviolet (buy) instruments in the cloudless atmosphere over clear ocean waters. A model accounting for this effect in buy measurements is developed and compared with observations from the Global Ozone Monitoring Experiment (GONE). The model extends existing models for ocean Raman scattering to the UV spectral range. Ocean Raman scattering radiance is propagated through the atmosphere using a concept of the Lambert equivalent reflectively and an accurate radiative transfer model for Rayleigh scattering. The model and observations can be used to evaluate laboratory measurements of pure water absorption in the UV. The good agreement between model and observations suggests that buy instruments may be useful for estimating chlorophyll content.
Spontaneous vibrational Raman scattering was used to measure temperature in an aviation combustor sector burning jet fuel. The inlet temperature ranged from 670 K (750 F) to 756 K (900 F) and pressures from 13 to 55 bar. With the exception of a discrepancy that we attribute to soot, good agreement was seen between the Raman-derived temperatures and the theoretical temperatures calculated from the inlet conditions. The technique used to obtain the temperature uses the relationship between the N2 anti-Stokes and Stokes signals, within a given Raman spectrum. The test was performed using a NASA-concept fuel injector and Jet-A fuel over a range of fuel/air ratios. This work represents the first such measurements in a high-pressure, research aero-combustor facility.
A Raman microscope has been coupled to a computer-controlled, two-dimensional linear translator attached to a custom-designed, sealed optical chamber to allow in situ acquisition of space-, and time-resolved spectra of an operating thin graphite/LiCoO2 Li-ion battery. This unique arrangement made it possible to collect continuously series of Raman spectra from a sharply defined edge of the battery exposing the anode (A), separator (S), and cathode (C), during charge and discharge, while the device was moved back and forth under the fixed focused laser beam along an axis normal to the layered A/S/C plane. Clear spectral evidence was obtained for changes in the amount of Li(+) within particles of graphite in the anode, and, to a lesser extent, of LiCoO2 in the cathode, during battery discharge both as a function of position and time. Analysis of time-resolved Raman spectro-micro-topography (SMT) measurements of the type described in this work are expected to open new prospects for assessing the validity of theoretical models aimed at simulating the flow of Li(+) within Li-ion batteries under operating conditions.
A high-performance spontaneous Raman scattering (SRS) system for measuring quantitative species concentration and temperature in high-pressure flames is now operational. The system is located in Glenn s Engine Research Building. Raman scattering is perhaps the only optical diagnostic technique that permits the simultaneous (single-shot) measurement of all major species (N2, O2, CO2, H2O, CO, H2, and CH4) as well as temperature in combustion systems. The preliminary data acquired with this new system in a 20-atm hydrogen-air (H2-air) flame show excellent spectral coverage, good resolution, and a signal-to-noise ratio high enough for the data to serve as a calibration standard. This new SRS diagnostic system is used in conjunction with the newly developed High- Pressure Gaseous Burner facility (ref. 1). The main purpose of this diagnostic system and the High-Pressure Gaseous Burner facility is to acquire and establish a comprehensive Raman-scattering spectral database calibration standard for the combustion diagnostic community. A secondary purpose of the system is to provide actual measurements in standardized flames to validate computational combustion models. The High-Pressure Gaseous Burner facility and its associated SRS system will provide researchers throughout the world with new insights into flame conditions that simulate the environment inside the ultra-high-pressure-ratio combustion chambers of tomorrow s advanced aircraft engines.
Narrow-band interference filters with improved transmission in the ultra-violet have been developed under NASA-funded research and used in the Raman Airborne Spectroscopic Lidar (RASL) in ground-based, upward-looking tests. Measurements were made of atmospheric water vapor, cirrus cloud optical properties and carbon dioxide that improve upon any previously demonstrated using Raman lidar. Daytime boundary and mixed layer profiling of water vapor mixing ratio up to an altitude of approximately 4 h is performed with less than 5% random error using temporal and spatial resolution of 2-minutes and 60 - 210, respectively. Daytime cirrus cloud optical depth and extinction-to-backscatter ratio measurements are made using 1 -minute average. Sufficient signal strength is demonstrated to permit the simultaneous profiling of carbon dioxide and water vapor mixing ratio into the free troposphere during the nighttime. A description of the filter technology developments is provided followed by examples of the improved Raman lidar measurements.
This paper explores the characterization of Kevlar composite materials using Raman spectroscopy. The goal of the research is to develop and understand the Raman spectrum of Kevlar materials to provide a foundation for the development of nondestructive evaluation (NDE) technologies based on the interaction of laser light with the polymer Kevlar. The paper discusses the fundamental aspects of experimental characterization of the spectrum of Kevlar, including the effects of incident wavelength, polarization and laser power. The effects of environmental exposure of Kevlar materials on certain characteristics of its Raman spectrum are explored, as well as the effects of applied stress. This data may provide a foundation for the development of NDE technologies intended to detect the in-situ deterioration of Kevlar materials used for engineering applications that can later be extended to other materials such as carbon fiber composites.
Methods and systems of the present invention identify the presence of and/or the concentration of a selected analyte in a subject by: (a) illuminating a selected region of the eye of a subject with an optical excitation beam, wherein the excitation beam wavelength is selected to generate a resonant Raman spectrum of the selected analyte with a signal strength that is at least 100 times greater than Raman spectrums generated by non-resonant wavelengths and/or relative to signals of normal constituents present in the selected region of the eye; (b) detecting a resonant Raman spectrum corresponding to the selected illuminated region of the eye; and (c) identifying the presence, absence and/or the concentration of the selected analyte in the subject based on said detecting step. The apparatus may also be configured to be able to obtain biometric data of the eye to identify (confirm the identity of) the subject.
Metal-doped sol-gel materials, suitable for use as sensors for surface-enhanced Raman spectroscopic analysis for trace chemical detection, are produced by effecting gelation and solvent removal of a doped sol-gel under mild temperature conditions. At least in certain instances reaction and drying will desirably be effected in an oxygen-starved environment. The metal of the sol-gel material functions, when irradiated, to produce a plasmon field for interaction with molecules of an analyte in contact therewith, increasing by orders of magnitude Raman photons that are generate by excitation radiation, and the method allows matching of the metal and metal particle size to a wavelength of light (or incident radiation, e.g., laser radiation) to generate surface plasmons. The porosity of the sol-gel material dramatically increases the surface area, and thereby the amount of metal exposed for analyte interaction. The sensors provided may be in the form of glass vials, fiber optics, multi-well micro-sample plates, etc., having surface coatings of the doped sol-gel material, to provide sampling systems for use in a Raman instrument.
A method of optical thermometry, now undergoing development, involves low-resolution measurement of the spectrum of spontaneous Raman scattering (SRS) from N2 and O2 molecules. The method is especially suitable for measuring temperatures in high pressure combustion environments that contain N2, O2, or N2/O2 mixtures (including air). Methods based on SRS (in which scattered light is shifted in wavelength by amounts that depend on vibrational and rotational energy levels of laser-illuminated molecules) have been popular means of probing flames because they are almost the only methods that provide spatially and temporally resolved concentrations and temperatures of multiple molecular species in turbulent combustion. The present SRS-based method differs from prior SRS-based methods that have various drawbacks, a description of which would exceed the scope of this article. Two main differences between this and prior SRS-based methods are that it involves analysis in the frequency (equivalently, wavelength) domain, in contradistinction to analysis in the intensity domain in prior methods; and it involves low-resolution measurement of what amounts to predominantly the rotational Raman spectra of N2 and O2, in contradistinction to higher-resolution measurement of the vibrational Raman spectrum of N2 only in prior methods.
Retrieval of water vapor mixing ratio using the Howard University Raman Lidar is presented with emphasis on three aspects: i) performance of the lidar against collocated radiosondes and Raman lidar, ii) investigation of the atmospheric state variables when poor agreement between lidar and radiosondes values occurred and iii) a comparison with satellite-based measurements. The measurements were acquired during the Water Vapor Validation Experiment Sondes/Satellites 2006 field campaign. Ensemble averaging of water vapor mixing ratio data from ten night-time comparisons with Vaisala RS92 radiosondes shows on average an agreement within 10 % up to approx. 8 km. A similar analysis of lidar-to-lidar data of over 700 profiles revealed an agreement to within 20 % over the first 7 km (10 % below 4 km). A grid analysis, defined in the temperature - relative humidity space, was developed to characterize the lidar - radiosonde agreement and quantitatively localizes regions of strong and weak correlations as a function of altitude, temperature or relative humidity. Three main regions of weak correlation emerge: i) regions of low relative humidity and low temperature, ii) moderate relative humidity at low temperatures and iii) low relative humidity at moderate temperatures. Comparison of Atmospheric InfraRed Sounder and Tropospheric Emission Sounder satellites retrievals of moisture with that of Howard University Raman Lidar showed a general agreement in the trend but the formers miss a lot of the details in atmospheric structure due to their low resolution. A relative difference of about 20 % is usually found between lidar and satellites measurements.
Raman spectra of ZnO and Co substituted Zn1-xCoxO (ZCO) were carried out using the Raman microprobe system with an p.,+ ion laser source of 514.5 nm wavelength. The shift towards the lower frequency side of the nonpolar E210w mode and the broadening due to Co substitution in ZnO were analyzed using the phonon confinement model. The magnetic measurements showed ferromagnetic behavior with the maximum saturation magnetization (1.2micron Beta/ErCo) for 10% Co substitution, which decreased wi th at further increase in Co concentrations. The intensities of E1(LO) at 584 cm-1 and multiphonon modes at 540 cm-1 were increased with an increase in Co substitution. The additional Raman modes in ceramic targets of ZCO spectra for higher concentration of Co substitution (x=15%-20%) were identified to be due to the spinel ZnCo2O4 secondary phase.
A chemical method of synthesis and application of coating materials that are especially suitable for surface-enhanced Raman spectroscopy (SERS) has been developed. The purpose of this development is to facilitate the utilization of the inherently high sensitivity of SERS to detect chemicals of interest (analytes) in trace amounts, without need for lengthy sample preparation. Up to now, the use of SERS has not become routine because the methods available have not been able to reproduce sampling conditions and provide quantitative measurements. In contrast, the coating materials of the present method enable analysis with minimum preparation of samples, and SERS measurements made using these materials are reproducible and reversible. Moreover, unlike in methods investigated in prior efforts to implement SERS, sampling is not restricted to such specific environments as electrolytes or specific solvents. The coating materials of this method are porous glasses, formed in sol-gel processes, that contain small particles of gold or silver metal. Materials of this type can be applied to the sample-contact surfaces of a variety of sampling and sensing devices, including glass slides, glass vials, fiber-optic probes, and glass tubes. Glass vials with their insides coated according to this method are particularly convenient for SERS to detect trace chemicals in solutions: One simply puts a sample solution containing the analyte(s) into a vial, then puts the vial into a Raman spectrometer for analysis. The chemical ingredients and the physical conditions of the sol-gel process have been selected so that the porous glass formed incorporates particles of the desired metal with size(s) to match the wavelength(s) of the SERS excitation laser in order to optimize the generation of surface plasmons. The ingredients and processing conditions have further been chosen to tailor the porosity and polarity of the glass to optimize the sample flow and the interaction between the analyte(s) and the plasmon field that generates Raman photons. The porous silica network of a sol-gel glass creates a unique environment for stabilizing SERS-active metal particles. Relative to other material structures that could be considered for SERS, the porous silica network offers higher specific surface area and thus greater interaction between analyte molecules and metal particles. Efforts to perform SERS measurements with the help of sampling devices coated by this method have been successful. In tests, numerous organic and inorganic chemicals were analyzed in several solvents, including water. The results of the tests indicate that the SERS measurements were reproducible within 10 percent and linear over five orders of magnitude. One measure of the limits of detectability of chemicals in these tests was found to be a concentration of 300 parts per billion. Further development may eventually make it possible to realize the full potential sensitivity of SERS for detecting some analytes in quantities as small as a single molecule.
An alternative optical thermometry technique that utilizes the low-resolution (order 10(exp 1)/cm) pure-rotational spontaneous Raman scattering of air is developed to aid single-shot multiscalar measurements in turbulent combustion studies. Temperature measurements are realized by correlating the measured envelope bandwidth of the pure-rotational manifold of the N2/O2 spectrum with a theoretical prediction of a species-weighted bandwidth. By coupling this thermometry technique with conventional vibrational Raman scattering for species determination, we demonstrate quantitative spatially resolved, single-shot measurements of the temperature and fuel/oxidizer concentrations in a high-pressure turbulent Cf4-air flame. Our technique provides not only an effective means of validating other temperature measurement methods, but also serves as a secondary thermometry technique in cases where the anti-Stokes vibrational N2 Raman signals are too low for a conventional vibrational temperature analysis.
The motivation of this work was to have robust spectroscopic sensors for sensitive detection and chemical analysis of organic and molecular compounds. The solution is to use silica sphere optical resonators to provide surface-enhanced spectroscopic signal. Whispering-gallery mode (WGM) resonators made from silica microspheres were used for surface-enhanced Raman scattering (SERS) without coupling to a plasmonic mechanism. Large Raman signal enhancement is observed by exclusively using 5.08-micron silica spheres with 785-nm laser excitation. The advantage of this non-plasmonic approach is that the active substrate is chemically inert silica, thermally stable, and relatively simple to fabricate. The Raman signal enhancement is broadly applicable to a wide range of molecular functional groups including aliphatic hydrocarbons, siloxanes, and esters. Applications include trace organic analysis, particularly for in situ planetary instruments that require robust sensors with consistent response.