Cold Neutron Prompt Gamma Activation Research Articles

Hydrogen pickup measurements in zirconium alloys: Relation to oxidation kinetics

The optimization of zirconium-based alloys used for nuclear fuel cladding aims to reduce hydrogen pickup during operation, and the associated cladding degradation. The present study focuses on precisely and accurately measuring hydrogen pickup fraction for a set of alloys to specifically investigate the effects of alloying elements, microstructure and corrosion kinetics on hydrogen uptake. To measure hydrogen concentrations in zirconium alloys two techniques have been used: a destructive technique, Vacuum Hot Extraction, and a non-destructive one, Cold Neutron Prompt Gamma Activation Analysis. The results of both techniques show that hydrogen pickup fraction varies significantly with exposure time and between alloys. A possible interpretation of the results is that hydrogen pickup results from the need to balance charge. That is, the pickup of hydrogen shows an inverse relationship to oxidation kinetics, indicating that, if transport of charged species is rate limiting, oxide transport properties such as oxide electronic conductivity play a key role in the hydrogen pickup mechanism. Alloying elements (either in solid solution or in precipitates) would therefore impact the hydrogen pickup fraction by affecting charge transport.

Weathering Patterns of Ignitable Liquids with the Advanced Distillation Curve Method.

One can take advantage of the striking similarity of ignitable liquid vaporization (or weathering) patterns and the separation observed during distillation to predict the composition of residual compounds in fire debris. This is done with the advanced distillation curve (ADC) metrology, which separates a complex fluid by distillation into fractions that are sampled, and for which thermodynamically consistent temperatures are measured at atmospheric pressure. The collected sample fractions can be analyzed by any method that is appropriate. Analytical methods we have applied include gas chromatography (with flame ionization, mass spectrometric and sulfur chemiluminescence detection), thin layer chromatography, FTIR, Karl Fischer coulombic titrimetry, refractometry, corrosivity analysis, neutron activation analysis and cold neutron prompt gamma activation analysis. We have applied this method on product streams such as finished fuels (gasoline, diesel fuels, aviation fuels, rocket propellants), crude oils (including a crude oil made from swine manure) and waste oils streams (used automotive and transformer oils). In this paper, we present results on a variety of ignitable liquids that are not commodity fuels, chosen from the Ignitable Liquids Reference Collection (ILRC). These measurements are assembled into a preliminary database. From this selection, we discuss the significance and forensic application of the temperature data grid and the composition explicit data channel of the ADC.

Cold neutron prompt gamma activation analysis, a non-destructive technique for hydrogen level assessment in zirconium alloys

We propose a novel use of a non-destructive technique to quantitatively assess hydrogen concentration in zirconium alloys. The technique, called Cold Neutron Prompt Gamma Activation Analysis (CNPGAA), is based on measuring prompt gamma rays following the absorption of cold neutrons, and comparing the rate of detection of characteristic hydrogen gamma rays to that of gamma rays from matrix atoms. Because the emission is prompt, this method has to be performed in close proximity to a neutron source such as the one at the National Institute of Technology (NIST) Center for Neutron Research. Determination shown here to be simple and accurate, matching the results given by usual destructive techniques such as Vacuum Hot Extraction (VHE), with a precision of ±2mgkg−1 (or wtppm). Very low levels of hydrogen (as low as 5mgkg−1 (wtppm)) can be detected. Also, it is demonstrated that CNPGAA can be applied sequentially on an individual corrosion coupon during autoclave testing, to measure a gradually increasing hydrogen concentration. Thus, this technique can replace destructive techniques performed on “sister” samples thereby reducing experimental uncertainties.

Relating Complex Fluid Composition and Thermophysical Properties with the Advanced Distillation Curve Approach

AbstractComplex fluids have long posed a significant challenge in our ability to characterize and model fluid properties. Here, we consider complex fluids to be mixtures with many components that can differ significantly in polarity and polarizability. The penultimate complex fluid is crude oil, although many other fluids such as finished fuels are also highly complex. We have recently introduced a measurement strategy that can simplify these efforts and provides the added potential of linking chemical composition (i.e. analytical) information with physical property information. In addition to chemical characterization, the approach provides the ability to calculate thermodynamic and transport properties for such complex heterogeneous streams. The technique is based on the advanced distillation curve (ADC) metrology, which separates a complex fluid by distillation into fractions that are sampled, and for which thermodynamically consistent temperatures are measured at atmospheric pressure. The collected sample fractions can be analyzed by any method that is appropriate. Analytical methods we have applied include gas chromatography (with flame ionization, mass spectrometric and sulfur chemiluminescence detection), thin‐layer chromatography, FTIR, Karl Fischer coulombic titrimetry, refractometry, corrosivity analysis, neutron activation analysis and cold neutron prompt gamma activation analysis. We have applied this method on product streams such as finished fuels (gasoline, diesel fuels, aviation fuels, rocket propellants), crude oils (including a crude oil made from swine manure) and waste oil streams (used automotive and transformer oils). In this review, we describe the essential features of the ADC metrology with illustrative examples.

Effects of sample and spectrum characteristics on cold and thermal neutron prompt gamma activation analysis in environmental studies of plants

Previous studies including the development of methods for the determination of carbon, nitrogen, and phosphorus in cattail using cold neutron prompt gamma activation (CNPGAA) and thermal neutron prompt gamma activation analysis (TNPGAA); evaluation of the precision and accuracy of these methods through the analysis of Standard Reference Materials (SRMs); and comparison of the sensitivity of CNPGAA to TNPGAA have been done in the CNPGAA and TNPGAA facilities at the National Institute of Standards and Technology (NIST). This paper integrates the findings from all of these prior studies and presents recommendations for the application of CNPGAA and TNPGAA in environmental studies of plants based on synergistic considerations of the effects of neutron energy, matrix factors such as chlorine content, Compton scattering, hydrogen content, sample thickness, and spectral interferences from Cl on the determination of C, N, and P. This paper also provides a new approach that simulates a sensitivity curve for an element of interest (S), which is a function of hydrogen content (X) and sample thickness (Y) as follows: S = aX + bY + c (where a, b, and c are constants). This approach has provided more accurate results from the analysis of SRMs than traditional methods and an opportunity to use models to optimize experimental conditions.

Combinatorial study of thin film metal hydride by prompt gamma activation analysis

Cold neutron prompt gamma activation analysis (PGAA) was used to determine the mass of hydrogen in Mg hydride thin films with varying hydrogenation times. The results suggest that hydrogenation of the Mg thin films remains unsaturated even after 48 h of treatment, contrary to the indications of inferential hydrogen measurement methods. To demonstrate PGAA as an effective combinatorial methodology for hydride thin films, a continuously varying composition gradient of thin MgyTi(1−y) hydride film with y ranging from 0.65 to 0.94 was prepared and analyzed by both PGAA and instrumental neutron activation analysis (INAA). The variation in the molar ratio of Mg, Ti, and H was obtained for nine 5 mm wide segments of the film.

Determination of carbon, nitrogen, and phosphorus in cattail using thermal neutron prompt gamma activation analysis

A method for the determination of carbon, nitrogen, and phosphorus in cattail using cold neutron prompt-gamma activation analysis (CNPGAA) has been developed and evaluated through the analysis of standard reference materials (SRM). After extensive preparation, approximately 400 mg cattail samples from the lower Apalachicola River floodplain were irradiated in the CNPGAA facility at the National Institute of Standards and Technology (NIST). The results of numerous field samples and two standard reference materials using the nuclear method show favorable comparison to results obtained by a CHNS/O analyzer.

Application of cold neutron prompt-gamma activation analysis in environmental studies of aquatic plants

This paper describes the use of cold-neutron prompt-gamma activation analysis (CNPGAA) to determine carbon, nitrogen, and phosphorus in the aquatic plant Typha domingensis, commonly known as cattail, during spring and fall seasons. According to studies of the Florida Everglades, cattail replaces sawgrass as a result of nutrient enrichment from farm water runoff. Nutrient enrichment, especially phosphorus, in sediment and the water column can lead to undesirable expansion. Early signs of this expansion are apparent in the Apalachicola River floodplain near Apalachicola, Florida, USA. This research project is designed to use cattails as biomonitors of nutrient enrichment in the lower Apalachicola River floodplain. Determination of carbon, nitrogen, and phosphorus in cattail using cold neutron prompt-gamma activation has been developed in our previous studies at the CNPGAA facility at the National Institute of Standards and Technology (NIST), USA. The results of numerous field samples, collected from the study area during spring and fall seasons in 2002, will be presented in this paper.

Incoherent neutron-scattering determination of hydrogen content: Theory and modeling

Hydrogen concentrations of 0 up to 350mg∕kg in a titanium alloy have been determined at National Institute of Standards and Technology (NIST) with neutron incoherent scattering (NIS) and with cold neutron prompt gamma activation analysis. The latter is a well-established technique, while the former was demonstrated earlier at NIST by counting the neutrons scattered under 45° or 60° and establishing a linear relationship between hydrogen concentration and count rate. In this paper, it is shown that the NIS response is complicated by the dependence of the apparent hydrogen scattering cross section on the sample temperature and the hydrogen chemical binding. It is demonstrated that detection of scattered neutrons at two different angles as well as a more complex theoretical approach (i.e., including Monte Carlo modeling with the free-gas model) are required to correctly interpret NIS measurements. As a result, the process of matching standards and samples becomes less critical.

Hydrogen content in doped and undoped BaPrO3 and BaCeO3 by cold neutron prompt-gamma activation analysis

Proton uptake in undoped and Y-doped BaPrO3 has been measured by cold neutron prompt-gamma activation analysis, and compared to the proton uptake in Gd-doped BaCeO3, as determined by the same technique. The conventional proton incorporation model of perovskites in which oxygen ion vacancies, generated by the introduction of the trivalent dopant onto the tetravalent perovskite site, are filled with hydroxyl groups upon exposure of the sample to H2O containing atmospheres, predicts that the proton concentration in such materials should be no greater than the dopant concentration. In contradiction to this model, the proton concentration in BaPr1−xYxO3 after humidification is as much as three times greater than the dopant concentration, and even undoped samples contain a high concentration of protons. Moreover, x-ray photoemission spectra suggest that the Pr oxidation state is lowered upon hydration. In contrast, BaCe0.9Y0.1O3 shows a typical hydrogen concentration, of close to 90% of the yttrium concentration. The results are interpreted in terms of the variable valence of Pr, which can become reduced from the 4+ to the 3+ oxidation state upon exposure to water, and effectively behaves as a self-dopant within the structure.

Non-Destructive Evaluation of Carbon Fiber Composite Reinforcement Content

The use of light-weight, high-strength composite materials in motors, generators, and energy storage devices has become common as a means to maximize energy density. To ensure reliability, non-destructive and destructive evaluation techniques have been employed to measure the mechanical properties of fabricated components. In carbon fiber-reinforced, polymer matrix composites, mechanical strength is primarily derived from the fiber volume fraction. Due to the lack of a nondestructive method, common techniques for fiber volume determination are currently destructive. In this investigation, a non-destructive method for the measurement of the fiber volume fraction of carbon fiber-reinforced, polymer matrix composites has been developed using cold neutron prompt gamma activation analysis (PGAA). Fiber volume determination is accomplished in this technique by measuring and comparing the carbon and hydrogen content in a given sample (or samples). PGAA is a nuclear analytical technique performed by exposing a sample to neutron radiation. PGAA measurements are non-destructive and can be performed without chemical preparation of the sample. Fiber volumes of several composite coupons have been determined relative to standard samples of known fiber volume and measurements are in good agreement with values predicted by acid digestion tests. Fiber volume measurement using PGAA can potentially be applied to any composite material where the contents of the matrix and reinforcement differ. The technique can also be spatially sensitive, with resolution limited by the dimensions of the neutron beam that is used.

Accurate absolute intensities for the 35Cl(n,γ) reaction gamma-ray standard

The absolute intensities of 36 γ-rays in the energy range of 292–8579 keV from neutron capture in chlorine were remeasured at the Budapest cold neutron prompt gamma activation analysis facility. The 1% level of accuracy of the nitrogen standard was practically achieved for the relative intensity of most of the 36Cl γ-rays, thus making chlorine a useful secondary standard for efficiency calibration of germanium detectors.

Cold neutron PGAA facility at Budapest

The new cold neutron prompt gamma activation analysis (PGAA) facility provides improved capabilities for routine prompt gamma analysis and for the investigation of radiative neutron capture. The versatile beam chopper makes possible time-of-flight measurements and the acquisition of prompt and decay spectra simultaneously. The chopped beam PGAA technique combines the advantages of the in-beam measurement and the greater simplicity of decay gamma spectra.

Performance of the University of Texas cold-neutron prompt gamma activation analysis facility

The University of Texas cold-neutron prompt gamma-activation analysis (PGAA) facility is operational at the 1-MW UT TRIGA research reactor. The UT-PGAA facility utilizes a guided cold neutron beam produced by the Texas Cold Neutron Source. The cold neutrons are transported to the PGAA chamber via a 6-m long curved neutron guide followed by an 80-cm long converging neutron guide. A program of testing, optimizing, and calibrating the UT-PGAA facility is currently underway. Preliminary results for the sensitivities and detection limits of boron, hydrogen, and silicon in semiconductor materials are given.

Standards for Hydrogen in Titanium Alloy

ABSTRACTMass-fraction standards of dilute hydrogen in titanium alloy are prepared by direct reaction of the elements, and verified by cold-neutron prompt-gamma activation analysis. The procedure is applied to the production and characterization of Standard Reference Materials.

Application of cold-neutron prompt gamma activation analysis at the University of Texas reactor

A cold-neutron prompt gamma activation analysis (PGAA) system is operational at the University of Texas (UT) 1 MW TRIGA research reactor. A 6 m long curved neutron guide followed by an 80 cm long converging (focusing) neutron guide transports cold neutrons from the Texas Cold Neutron Source to the PGAA chamber. The UT-PGAA system will be used to determine hydrogen and boron in semiconductor materials, gadolinium in neutron capture therapy samples, and multielementals in environmental and industrial samples.

Determination of hydrogen in titanium alloys by cold neutron prompt gamma activation analysis

Cold neutron prompt gamma-ray activation analysis (CNPGAA) has proven useful for the analysis of hydrogen in titanium alloys. The analysis is nondestructive, measures the entire sample, and the results are independent of the chemical form of hydrogen present. We have used the technique to measure H mass fractions as low as 50 mg/kg in titanium-alloy jet-engine compressor blades and to measure hydrogen in standards for neutron tomography.

Investigation of the hydrogen uptake of doped SrCeO 3 by TEM, thermogravimetry and cold neutron prompt gamma activation analysis (CNPGAA)

The microstructure of doped strontium cerate was studied by transmission electron microscopy (TEM). Using thermogravimetry (TG) the temperature dependence of water uptake in atmospheres with different water and oxygen pressures was examined in situ. Absolute hydrogen contents of precharged samples were obtained by cold neutron prompt gamma activation analysis (CNPGAA).

Cold neutron prompt gamma activation analysis at NIST: A progress report

An instrument for prompt gamma-ray activation analysis is now in operation at the NIST Cold Neutron Research Facility (CNRF). The cold neutron beam is relatively free of contamination by fast neutrons and reactor gamma rays, and the neutron fluence rate is 1.5·108 cm−2·s−1 (thermal equivalent). As a result of a compact target-detector geometry the sensitivity is better by a factor of as much as seven than that obtained with an existing thermal instrument, and hydrogen background is a factor of 50 lower. We have applied this instrument to multielement analysis of the Allende meteorite and other materials.

Measuring hydrogen by cold-neutron prompt-gamma activation analysis

By irradiating with cold neutrons and avoiding hydrogenous materials of construction, we have developed a PGAA instrument at the Cold Neutron Research Facility at NIST with hydrogen detection limits in the microgram range in many materials. Quantities of 5–10 μg H/g are presently measurable in gram-sized samples of silicon or quartz, and of order 0.01 wt % can be quantitatively measured in complex silicate rocks.