Year of fee payment : 8. Year of fee payment : A device and method for identifying the composition of a target sample. The target sample may be a matrix such as a metal alloy, a soil sample, or a work of art. The device includes an x-ray fluorescence detector that produces an x-ray signal output in response to the target sample.
The device also includes an optical spectroscope that produces an optical signal output in response to the target sample. Further, a processor is included that analyzes and combines the x-ray signal output and the optical signal output to determine the composition of the test material. In one embodiment, the optical spectroscope is a laser induced photon fluorescence detector.
Provisional Patent Application No. The present invention relates to devices for determining the composition of a test material and more specifically devices that use multiple fluorescence techniques for determining composition.
As a general rule, XRF is useful for all elements heavier than about titanium. In special cases, XRF is effective for measuring the fractional weight of lighter elements; for example, sulphur in oil is easily quantified. However, the method ceases to have any quantitative value for carbon, oxygen, fluorine and sodium and other very light elements.
To give a useful measure of these and other light elements, the preferred in situ method is optical spectroscopy.
Optical spectroscopy is a known technique for determining elemental and chemical compositions. Almost all portable optical spectroscopy systems currently available for measuring the elemental composition of alloys use a spark discharge to excite the optical spectrum to be analyzed. In recent years, lasers have been used to induce plasmas that result in fluorescent optical and near ultra-violet spectra.
Variations of the basic technique involve different lasers and different spectrometers. The formed plasma may be of millimeter or micron size and the optical spectra may be viewed over i microseconds or time-resolved in nanoseconds. The general technique is often referred to as laser-induced breakdown spectroscopy or LIBS, though sometimes it is referred to as laser-induced photon spectroscopy or LIPS. LIPF applies to any laser method for inducing photon spectra, from the infrared to the near ultra-violet, which results in the identification of the elements or compounds in any sample matrix.
Among other things, this fluorescence is linearly dependent on the absorber number density. Typically, single-interaction fluorescence occurs at wavelengths greater than or equal to the laser wavelength, and again for atoms and diatomic molecules especially, discrete fluorescence transitions may be observed.
LIPF while producing single-interaction fluorescence, more generally produces a high-temperature plasma in which atoms are excited to higher energies than the energy of the laser photons so that lower wave-length transitions are observed. Massachusetts Institute of Technology, indexed OcolC which is attached hereto as appendix A and is incorporated by reference herein in its entirety.
LIPF has the potential to measure the distribution of almost all elements in any matrix. In practice, the method has commercial sensitivity for a subset of elements, though with the proper choice of laser, that subset can encompass the most important light elements in a given application.
LIPF, however, has the general drawback that the efficiency of production of the optical emissions, that is, the intensities of the induced spectral lines, depends strongly on the matrix and the measuring conditions. Comparison standards are essential. Although both LIPF and XRF are known techniques, the techniques have not been combined into a single device to produce a more complete composition of a test material. Further, the measurements have not been graphically combined and scaled to provide a spectral representation on a graphical display device.
In a first embodiment of the invention there is provided a device for identifying the composition of a target sample. The x-ray fluorescence detector is sensitive to elements above a particular threshold. In general the threshold element is titanium. The laser induced photon detector is sensitive to the lighter elements below the threshold that typically include sodium, carbon and oxygen.
The processor receives the output signals from the x-ray fluorescence detector and the laser induced photon detector and begins to analyze the data. The analysis determines the type of material that is being processed, such as, a metal alloy that is an aluminum alloy. The processor then compares the data from the output signals concerning the common element and then scales the optical signal output data to produce a displayable output that contains the concentrations of elements within the test material.
In one embodiment, the x-ray fluorescence detector, the optical spectroscope and the processor are contained within a single housing. In other embodiments, the x-ray fluorescence detector and the optical spectroscope are not in the same housing, yet share a common processor.
In general, the data that is contained within the optical signal output is relative data concerning the concentrations of elements in the test sample, while the data that is contained within the x-ray signal output is absolute. To produce an output signal which can be displayed and which provides data regarding the concentration of elements in the test material, both the laser induced photon fluorescence detector and the x-ray fluorescence detector are sensitive to at least one common element within the target sample.
The processor uses data from the optical signal output and the x-ray signal output about the common element to normalize data contained within the optical signal output.
In another embodiment, the laser induced photon detector and the x-ray fluorescence detector are positioned within the device so that both analyze a common area of the target sample. The two detectors within the device may operate simultaneously in one embodiment to produce their respective output signals that are transferred to the processor. In another embodiment, the x-ray fluorescence detector operates first.
In the preferred embodiment, the length of time that it takes to measure the test material is shorter than the time for removal of the test material from the device and insertion of the test material in a second device for analysis.
Further, the device can be sized to be both portable and battery operated. The foregoing features of the invention will be more readily understood by reference to the following detailed description, taken with reference to the accompanying drawings, in which: []. I is a device [] for determining the composition of a test material such as a metal alloy, soil, artwork or any matrix.
The two detectors are electrically coupled to an analysis processor 8. The analysis processor 8 receives measurement signals from the XRF detector 2 and the LIPF detector 4 and analyzes the produced data to determine the elements which are the composition of the test material. The LWPF 4 detector may use either continuous or time-resolved spectroscopy.
In other embodiments, the measurements occur simultaneously. Preferably, the detectors work in conjunction such that the measurements take place during an interval which is less than the time it would take to remove the test sample from an XRF detector and place the test sample in a separate LIPF detector. In other embodiments, the laser of the LIPF detector may be separated from the XRF detector, but still shares a common analysis processor and display device. The measurements are made consistent by complementary information which is used to normalize the results such that a single graphical display may identify the elemental distributions that compose the target sample.
Coupled to the processor in various embodiments is memory which provides for the storage and future retrieval of the data which represents the composition of the test material. The XRF detector [] 2 and the LIPF detector 4 view a common target area 6 ; the area struck by the x-ray beam 14 overlaps the much smaller area struck by the laser beam Although in other embodiments, separate processors may be provided for both the XRF detector 2 and the LIPF detector 4 if the detectors operate simultaneously.
The XRF unit [] 2 includes an x-ray or gamma ray source 10 , which may be a radioactive source or an x-ray tube. The emitted radiations 14 strike the sample 6 inducing fluorescent radiation 16 that are detected in the suitable detector The detected events are processed in the pulse processor 20 , and the results of the distribution of pulse strengths sent to the analysis processor 8. The LIPF unit [] 4 includes a laser 22 whose beam 24 is focused by a lens system 26 onto the target 6.
It includes a Nd:YAG laser whose primary frequency is quadrupled to produce an excitation frequency of nm that can be used for creating a plasma that results in the nm fluorescence line for carbon. It should be understood by one of ordinary skill in the art that other lasers may be used which are capable of producing fluorescence lines for desired elements. The fluoresced spectrum [] 28 is captured into the spectrometer 32 by a lens system The analysis included low- from where they could possibly originate, unless power digital microscopy to assess paste the whole vessel was proven non-local.
This is followed vessels' surface. These techniques are non by a presentation of the results, which are then destructive and complement each other. The Japanese analysis had been performed. This analysis was Kuntur Wasi Archaeological Project excavated initiated to further our understanding of the the site from to , and again in , technological knowledge the ancient potters had , and Location of Kuntur Wasi and area of study. Original map drawn by Kinya Inokuchi, Eisei Tsurumi and Yuko Ito, modified with permission to show the main sites mentioned in the text.
Comparison with local geology, et al. A shift in architecture happens geological samples, and modern ceramics during the second phase, the Kuntur Wasi phase, allowed us to see that 1 most of the ceramics with a new large-scale architectural complex, were local productions, 2 different potting stone monoliths, water canals, special burials, traditions co-existed, and 3 ceramic and stylistic changes in the ceramic repertoire production and distribution evolved, with a [4] Inokuchi, , [7] ; [6] Onuki et al.
The next phase Copa phase witnessed archaeological phases at the site, and intensive, an intensification of building activity, and a local production later. The local tradition, larger population, with more people involved in continuing throughout the existence of the site, activities related to the temple, including is characterized by the use of volcanic probably ceramic manufacture.
During the final pyroclastic material mined from deposits in the architectural subphase of the Copa phase the nearby mountain, 8 km north of the site.
The major part of the ceremonial architecture was other main potting community appears later abandoned, and during the Sotera phase Kuntur and is very active during the third Wasi ceased to function as a ceremonial center. During the first derive from the use of local quaternary sand two archaeological phases Idolo and Kuntur deposits.
The nonlocal pastes present material Wasi foreign ceramics are found along with which outcrop in the middle coastal local productions. During the third phase Copa Jequetepeque Valley below or from the ceramic imports decreased, and a new potting Cajamarca basin, east of the site.
Production degraded during the fourth and presence of multiple production units [3] phase Sotera , when the site ceased to function Druc et al. Yoshio Onuki, Dr. The samples were examined would not require damaging the sample. The later analyzed with Raman microscopy which mineral analysis was done with a portable yields information about the minerals and digital microscope DinoLite in reflective light oxides present in the sample.
This allowed us to assess paste In both techniques, the ceramic fragment is composition and texture whenever possible, simply laid on a surface or deposited in the classifying the samples according to the chamber of the instrument.
The samples were petrographic groups identified in the prior analyzed at the laboratories of the Pontificia analyses briefly described above. The experimental conditions were with superficial oxidation at the end of the 40 kV, Raman firing.
Many present local, volcanic or analyses were carried out with a Renishaw Invia subvolcanic compositions. A few others seem to Raman spectrometer nm diode laser or have intrusive rock fragments, a material nm argon ion laser in conjunction with identified in our earlier analysis as indicative of WiRE 3. These attributions should Table1. Samples analyzed, surface and cross section views, reflected light microscopy. In sample RA10, the red contains both iron and manganese Mn , which Table 2 presents the chemical elements detected is fairly common.
Iron oxides can also yield with pXRF and minerals identified with Raman yellows. This depends upon firing and the type microscopy. Not all pigments could be of iron oxide used. In two cases, calcite appears identified as their Raman signal was not strong to have been preferred or used for obtaining a enough.
These could be done. Also, pXRF easily picks up are two bowls of the Copa phase third signals from the surface or slip beneath the archaeological phase at the site.
For the pigment if the pigment layer is too thin. This production of white, titanium oxide in the form would explain the differences between the of anatase is the most frequent mineral used. Even so but this signal may rather relate to the pXRF detected Fe, we are confident that the ferruginous, oxidized paste or slip underneath. Raman identification of graphite is correct in For nearly all samples, the red and black tones view of the style of the vessels Rojo Grafitado.
We do not know which medium or Ochre and calcite are local minerals. Pigment composition in the samples studied. Detection limits are dependant on the elements present but are in the ppb to ppm range. X-ray diffraction From powders and solids to thin films and nanomaterials In materials research, the scientist has many analytical questions related to the crystalline constitution of material samples. XRD is the only laboratory technique that reveals structural information, such as chemical composition, crystal structure, crystallite size, strain, preferred orientation and layer thickness.
Materials researchers therefore use XRD to analyze a wide range of materials, from powders and solids to thin films and nanomaterials.
Innovations in X-ray diffraction closely follow the research on new materials, such as in semiconductor technologies or pharmaceutical investigations. Industrial research is directed towards ever-increasing speed and efficiency of production processes.
Fully automated X-ray diffraction analysis in mining and building materials production sites results in more cost-effective solutions for production control. Solutions for analytical questions X-ray diffraction analysis meets many of the analytical needs of a materials scientist.
In powders, chemical phases are identified qualitatively as well as quantitatively. High- resolution X-ray diffraction reveals the layer parameters such as composition, thickness, roughness and density in semiconductor thin films. Small-angle X-ray scattering and pair distribution function PDF analysis help to analyze the structural properties of nano materials. Stresses and preferred orientation can be determined in a wide range of solid objects and engineered components.
X-ray fluorescence XRF spectrometry is an elemental analysis technique with broad application in science and industry. XRF is based on the principle that individual atoms, when excited by an external energy source, emit X-ray photons of a characteristic energy or wavelength.
By counting the number of photons of each energy emitted from a sample, the elements present may be identified and quantities. Henry Moseley was perhaps the father of this technique, since he, building on W. In Coster and Nishina were the first to use primary X-rays instead of electrons to excite a sample. In , the lithium drifted silicon detector was developed, and this technology is still in use today Jenkins The analysis is rapid and usually sample preparation is minimal or not required at all.
These instruments are used primarily for the provenance research on obsidian artifacts from around the world, but they are also used in special circumstances for the non-destructive analysis of other materials such as metals, ceramic paints, and soils. This small beam passes the sample holder carrying the sample at a very small angle 0. The main difference with respect to common XRF spectrometers is the use of monochromatic radiation and the total reflection optic.
Illuminating the sample with a totally reflected beam reduces the absorption as well as the scattering of the beam in the sample and its matrix. For this purpose the usage of trays with a diameter of 30mm, made of acrylic or quartz glass is common.
Liquids can be perpetrated directly on the sample tray. Powdered samples suspended matter, soils, minerals, metals, pigments, biogenous solids etc. In a similar way the direct preparation of single micro samples particles, slivers etc. Alternatively, powdered solids can be prepared as a suspension with volatile solvents like acetone or methanol. The suspension is then pipetted onto the sample tray. Analysis and quantification: In general all elements starting from Sodium up to Uranium excl.
Therefore, an element, which is not present in the sample, must be added for quantification Figure 3. All detectable elements are measured simultaneously. The net intensities of the element peaks are calculated with regard to corrections of line overlaps, background factors, escape peak correction etc.
It is completely independent of any cooling media and therefore applicable for on-site analysis.
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