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At least 19 records

Chemiluminescence Measurements in a Combustor Using a 7-Point Lean Direct Injector Array Configuration for Gas Turbine Engine Applications

Two different configurations of a 7-point lean direct injector array were investigated. Chemiluminescence images of C2* or CH* were collected during combustion tests for insight on flame structure for the two configurations. Several inlet conditions were tested by varying the equivalence ratio or reference velocity. For the center right-hand 60 degree and outer right-hand 52 degree outers, the chemiluminescence emanating from the central pilot appeared well isolated from the outers. At the same time, a hollow region below the pilot showed little fluctuation of chemiluminescence where a central recirculation zone was present during the non-reacting tests. The central left-hand 60 degree and outer right-hand 52 degree configuration displayed a narrower structure from the pilot compared to the flatter pilot observed in the other configuration. Additionally, the right-handed outer swirlers may be responsible for the asymmetry observed with the chemiluminescence images. Both configurations showed less variation in chemiluminescence intensity as the reference velocity was increased. This was likely due to better atomization and vaporization associated with higher fuel and air flow rates.

lean direct injection

Chemiluminescence Study of the Autoxidation of cis-1,4-Polyisoprene

The free-radical mechanism for the autoxidation of cis-1,4-polyisoprene (natural rubber or its synthetic counterpart) has been investigated extensively. An important feature of this mechanism, and indeed also of the autoxidation of hydrocarbons generally, is that it is a chain process propagated by alkyl and peroxy radicals and terminated through bimolecular reactions involving these same radicals. In the usual oxidation situation, that is, at all oxygen pressures greater than a few torr, the alkyl radicals are rapidly converted to peroxy radicals, and the termination step proceeds almost exclusively through the latter radicals. The bimolecular decay of the peroxy radicals is accompanied by a weak emission of light or chemiluminescence. Kinetic evidence is consistent with an electronically excited ketone produced in the termination reaction as the source of the emission. The first observation of chemiluminescence from the oxidative degradation of polymers was reported by Ashby, who dealt mainly with polypropylene but made passing mention of several other polymers. Subsequently, a number of papers have appeared dealing with oxidative chemiluminescence from a variety of polymers. In this paper we report the first detailed study of the chemiluminescence emitted in the autoxidation of cis-1,4-polyisoprene. The chemiluminescence technique is extremely sensitive and can follow rates of oxidation that are too slow to be measured conveniently by other means. This work thus offered the potential of throwing new light on the autoxidation of cis-1,4-polyisoprene, especially in the very early stages or under ambient conditions where conventional spectroscopic procedures are rather insensitive.

Mendenhall, G. David

Applications of chemiluminescence to bacterial analysis

Luminol chemiluminescence method for detecting bacteria was based on microbial activation of the oxidation of the luminol monoanion by hydrogen peroxide. Elimination of the prior lysing step, previously used in the chemiluminescence technique, was shown to improve considerably the reproducibility and accuracy of the method in addition to simplifying it. An inexpensive, portable photomultiplier detector was used to measure the maximum light intensity produced when the sample is added to the reagent. Studies of cooling tower water show that the luminol chemiluminescence technique can be used to monitor changes in viable cell population both under normal conditions and during chlorine treatment. Good correlation between chemiluminescence and plate counts was also obtained in the analysis of process water used in paper mills. This method showed good potential for monitoring the viable bacteria populations in activated sludge used in waste treatment plants to digest organic matter.

Searle, N. D.

Chemiluminescence Study on Thermal Degradation of Aircraft Tire Elastomers

Since the autoxidative process accounts in part for the degradation of rubber, including aircraft tires, it was felt that a study of the chemiluminescence from unsaturated elastomers could contribute significantly to an understanding of the degradation mechanism. The study revealed similarities in chemiluminescence behavior between four elastomers which were investigated, and it shows that similar oxidation mechanisms occur. Oxidative chemiluminescence was observed from purified samples of cis-1,4-polybutadiene, cis-1,4-polyisoprene, trans-polypentenamer, and 1,2-polybutadiene in an oxygen atmosphere at 25-150 C. The elastomer samples were placed in a 600 watt oven which is equipped with gas inlets for introducing any desired atmosphere. Chemiluminescence emission from the samples was focused with a two inch quartz lens onto the detector of a 12" photomultiplier which is connected to a photon counter. A strip-chart recorder, connected to the counter, permitted automatic data collection. Diagrams of the apparatus are included. The chemical reactions which occurred from the thermal decomposition of the polymer samples are described, and results (and tabulated data) are discussed.

Mendenhall, G. D.

Aqueous nitrite ion determination by selective reduction and gas phase nitric oxide chemiluminescence

An improved method of flow injection analysis for aqueous nitrite ion exploits the sensitivity and selectivity of the nitric oxide (NO) chemilluminescence detector. Trace analysis of nitrite ion in a small sample (5-160 microL) is accomplished by conversion of nitrite ion to NO by aqueous iodide in acid. The resulting NO is transported to the gas phase through a semipermeable membrane and subsequently detected by monitoring the photoemission of the reaction between NO and ozone (O3). Chemiluminescence detection is selective for measurement of NO, and, since the detection occurs in the gas-phase, neither sample coloration nor turbidity interfere. The detection limit for a 100-microL sample is 0.04 ppb of nitrite ion. The precision at the 10 ppb level is 2% relative standard deviation, and 60-180 samples can be analyzed per hour. Samples of human saliva and food extracts were analyzed; the results from a standard colorimetric measurement are compared with those from the new chemiluminescence method in order to further validate the latter method. A high degree of selectivity is obtained due to the three discriminating steps in the process: (1) the nitrite ion to NO conversion conditions are virtually specific for nitrite ion, (2) only volatile products of the conversion will be swept to the gas phase (avoiding turbidity or color in spectrophotometric methods), and (3) the NO chemiluminescence detector selectively detects the emission from the NO + O3 reaction. The method is free of interferences, offers detection limits of low parts per billion of nitrite ion, and allows the analysis of up to 180 microL-sized samples per hour, with little sample preparation and no chromatographic separation. Much smaller samples can be analyzed by this method than in previously reported batch analysis methods, which typically require 5 mL or more of sample and often need chromatographic separations as well.

NASA Discipline Environmental Health

Flame stabilization in DME spray flames under engine-relevant conditions characterized by OH* chemiluminescence and formaldehyde laser-induced fluorescence

The transient and quasi-steady flame structures of Dimethyl Ether (DME) fuel sprays, produced by a single-hole injector (Spray D), were investigated using Planar Laser-Induced Fluorescence (PLIF) and chemiluminescence imaging in a constant-volume chamber under Engine Combustion Network (ECN) Spray A conditions (900 K ambient temperature, 60 bar ambient pressure, 1500 bar injection pressure, and 22.8 kg/m 3 ambient density). Low-temperature chemical reaction zones were visualized using formaldehyde (CH 2 O) PLIF with 355 nm excitation, while high-temperature flame regions were captured via chemiluminescence imaging of excited-state hydroxyl radicals (OH*). Both transient and quasi-steady flame structures clearly show the transition from CH 2 O to OH*, highlighting the progression from low- to high-temperature combustion, while the position of the flame is displaced for DME compared to reference hydrocarbon n-dodecane. Homogeneous reactor calculations with detailed chemistry and using adiabatic mixing for initial temperature show that CH 2 O peaks are significantly higher for DME at the same equivalence ratio, with a higher heat-release during the cool-flame regime with respect to the fuel heating value. Thus, the cool-flame dynamic as a precursor to high-temperature combustion and flame stabilization exhibit distinct behavior for DME relative to conventional hydrocarbons, and these phenomena are effectively resolved through the soot-free nature of DME and the high-speed, time-resolved diagnostics.

CH2O laser-induced fluorescence

Chemiluminescence Measurements in a Combustor Using a 7-Point Lean Direct Injector Array Configuration for Gas Turbine Engine Applications

This paper reports results for a 7-point lean direct injector (LDI) array for a particular configuration. The LDI configuration in this study used a 60 degrees center pilot swirler and 52.5 degrees on the six outer swirlers. Chemiluminescence images of C2 and CH were collected at a frame rate of 25 Hz using an intensified CCD camera. Narrow bandwidth filters were coupled with the CCD camera in order to spectrally isolate C2 and CH signals. C2 was captured at 515 nm, and the CH signal was acquired at 430 nm. Six inlet conditions were considered in this study, all with the same inlet pressure, 75 psia, and same inlet temperature, 800 degcrees Fahrenheit. These conditions aimed to observe the effect of equivalence ratio, fuel staging, and reference velocity on C2 and CH emissions. Based on the chemiluminescence images, the changes in the inlet conditions was evident in both the pilot and outers. Additionally, the pilot (center injector element) appeared well isolated from the six outer elements under all test conditions.

lean direct injection

Development of a chemiluminescent and bioluminescent system for the detection of bacteria in wastewater effluent

Automated chemiluminescent and bioluminescent sensors were developed for continuous monitoring of microbial levels in wastewater effluent. Development of the chemiluminescent system included optimization of reagent concentrations as well as two new techniques which will allow for increased sensitivity and specificity. The optimal reagent concentrations are 0.0025 M luminol and 0.0125 M sodium perborate in 0.75N sodium hydroxide before addition of sample. The methods developed to increase specificity include (1) extraction of porphyrins from bacteria collected in a filter using 0.1N NaOH - 50 percent Ethanol, and (2) use of the specific reaction rate characteristics for the different luminol catalysts. Since reaction times are different for each catalyst, the reaction can be made specific for bacteria by measuring only the light emission from the particular reaction time zone specific for bacteria. Developments of the bioluminescent firefly luciferase system were in the area of flow system design.

Thomas, R. R.

Interferences in the chemiluminescent measurement of NO and NO2 emissions from combustion systems

Two factors which may affect the quantification of NO and NO2 concentrations when using chemiluminescent analysis are investigated. The first is the dependence of the chemiluminescent intensity on competing third body quenching reactions. Relative quenching efficiencies are determined as a function of third body concentration for six different species which are common products of combustion. A mathematical expression is derived which allows calculation of the actual concentration of NO given the indicated concentration of NO and the concentrations of the important third bodies. An example calculation is presented. The second factor which is investigated involves the conversion of low molecular weight nitrogen containing species, other than NO2, in commercial NOx converters. Conversion efficiencies for six species were determined using a commercial stainless steel catalyst at 923 K.

Matthews, R. D.

Modified chemiluminescent NO analyzer accurately measures NOX

Installation of molybdenum nitric oxide (NO)-to-higher oxides of nitrogen (NOx) converter in chemiluminescent gas analyzer and use of air purge allow accurate measurements of NOx in exhaust gases containing as much as thirty percent carbon monoxide (CO). Measurements using conventional analyzer are highly inaccurate for NOx if as little as five percent CO is present. In modified analyzer, molybdenum has high tolerance to CO, and air purge substantially quenches NOx destruction. In test, modified chemiluminescent analyzer accurately measured NO and NOx concentrations for over 4 months with no denegration in performance.

Summers, R. L.

Biological water quality monitoring using chemiluminescent and bioluminescent techniques

Automated chemiluminescence and bioluminescence sensors were developed for the continuous monitoring of microbial levels in water supplies. The optimal chemical procedures were determined for the chemiluminescence system to achieve maximum sensitivity. By using hydrogen peroxide, reaction rate differentiation, ethylene diamine tetraacetic acid (EDTA), and carbon monoxide pretreatments, factors which cause interference were eliminated and specificity of the reaction for living and dead bacteria was greatly increased. By employing existing technology with some modifications, a sensitive and specific bioluminescent system was developed.

Thomas, R. R.

Interferences in chemiluminescent measurement of NO and NO2 emissions from combustion systems

Two factors that may affect the quantification of NO and NO2 concentrations when using chemiluminescent analysis are investigated. The first is the dependence of the chemiluminescent intensity on competing third body quenching reactions. Relative quenching efficiencies are determined as a function of third body concentration for six different species that are common products of combustion. A mathematical expression is derived that allows calculation of the actual concentration of NO, given the indicated concentration of NO and the concentrations of the important third bodies. An example calculation is presented. The second factor investigated involves the conversion to NO of low molecular weight nitrogen-containing species, other than NO2, in commercial NOx converters. Conversion efficiencies for six species are determined using a commercial stainless steel catalyst at 920 K.

Matthews, R. D.

Recent assessment of the performance and accuracy of a chemiluminescent rocket sonde for upper atmospheric ozone measurements

The chemiluminescent rocket ozonesonde utilizing rhodamine-B as a detector and self-pumping for air sampling has been improved. The instrument employs standard meteorological sounding systems and is the only technique available for routine nighttime ozone measurements above balloon altitudes. The chemiluminescent detector, when properly calibrated, is shown to be specific to ozone, stable, and of sufficient sensitivity for accurate measurements of ozone from about 65-20 km. An error analysis indicates that the measured ozone profiles have an absolute accuracy of about + or - 12% and a precision of about + or - 6%. Approximately 20 flights have been conducted for geophysical investigations, while additional flights were conducted with other rocket and satellite ozone soundings for comparisons. In general, these comparisons showed good agreement.

Hilsenrath, E.

Satellite and correlative measurements of stratospheric ozone - Comparison of measurements made by SAGE, ECC balloons, chemiluminescent, and optical rocketsondes

The validity of ozone-profile data from the satellite sensor SAGE was tested in a series of correlative experiments conducted at five fixed sites between 6 deg S and 65 deg N during 1979-1980. The intercomparisons included data taken with electrochemical ozone (ECC) balloonsondes and chemiluminescent and optical rocketsondes. The average mean difference for 17 separate comparisons between the SAGE and ECC balloonsonde observations over the altitudes 18-28 km was 9.3 percent with a standard deviation of 2.8 percent. Excluding comparisons separated by greater than 500 km reduces the average mean difference to 8.9 percent and the standard deviation to 2.1 percent. The average mean difference between SAGE and three optical rocketsonde observations over the altitudes 25-50 km was 11 percent, and between SAGE and two chemiluminescent rocketsondes over the altitudes 20-60 km it was 13.5 percent. Considering the differences in vertical resolution, experimental errors, and ozone time and space gradients, the agreement between SAGE-derived ozone profiles and these correlative measurements is considered very good. In addition, isopleths of ozone mixing ratio versus latitude and altitude are in good agreement with previously published results.

Mccormick, M. P.

Low-Temperature Chemiluminescence From cis-1,4-Polybutadiene, 1,2-Polybutadiene, and trans-Polypentenamer at Temperatures Near Ambient

The chemiluminescence emission at 25-60 C was measured from films of cis-1,4-polybutadiene, 1,2-polybutadiene, and trans-polypentenamer. The polymers were autoxidized previously in air 100 C, or allowed to react with singlet molecular oxygen in solution, and then cast into films. Values of beta(or k(sub d,((1)O2 yields (3)03)/k(sub r)((1)O2 + polymer yields products)) were determined in benzene for cis-1,4-polybutadiene and cis-1,4-polyisoprene, and for model compounds cis-3-hexene and cis-3-methyl-3-hexene by independent methods. The chemiluminescence emission from irradiated films of the polymers containing a dye sensitizer showed a complicated time dependence, and the results depended on the length of irradiation.

Nathan, Richard A.

Aqueous chemiluminescent systems

This invention relates to novel water-soluble esters of oxalic acid, and to compositions that are useful for generating chemiluminescent emission by reacting said esters of oxalic acid with hydrogen peroxide in the presence of water and a fluorescent compound, and to a process for generating chemiluminescent emission by using said compositions.

Mohan, Arthur Gaudens

Simultaneous 100-kHz Acetone Planar Laser-Induced Fluorescence and OH* Chemiluminescence in a Linear Non-Premixed Detonation Channel

Reactant mixing and combustion are investigated in an optically accessible, self-excited linear detonation combustor. The mixing field is captured using 100 kHz planar laser-induced fluorescence (PLIF) imaging of acetone as a tracer in the fuel supply, while 100 kHz chemiluminescence imaging of excited-state hydroxyl (OH*) radicals simultaneously resolves the evolution of the detonation wave. Time sequences are acquired over multiple detonation cycles in each test, with acetone-PLIF images collected along multiple orthogonal planes to reveal the complex three-dimensional topography of the fuel distribution. The instantaneous and phase averaged acetone-PLIF images enable measurement of key fuel injection characteristics, such as the injector recovery time, fuel jet velocity, and refill height for a range of operating conditions. Instantaneous and phase-averaged measurements of acetone-PLIF with the time-coincident OH* chemiluminescence images also reveal a number key features, such as fuel stratification and weak detonation in the injector near field, incomplete combustion and deflagration behind the detonation wave, vitiation and deflagration of reactants ahead of the detonation wave, and fuel and oxidizer recovery time mismatch leading to combustion inefficiency. These measurements significantly enhance the ability to obtain detailed information on the intracycle and intercycle spatiotemporal evolution of the reactant refill process and its coupled effects on the detonation wave structure and propagation.

Propulsion