LABORATORY 1: XRF SPECTROSCOPY

DEPARTMENT OF MECHANICAL ENGINEERING

Author: UVic Mech Student Class: Instructor: T.A: Date: Total Pages: Mech 285 B03 UVic Mech Proffs UVic Mech TA 18-Jul-2011 11

Laboratory 1: XRF Spectroscopy

Ref: Mech 285-0101 Date: 18-Jul-2011

Summary
The non destructive method of elemental identification called X-ray fluorescence spectroscopy (XRF) was introduced and then used to determine the chemical make-up of items. X-ray fluorescence spectroscopy was used to determine the elemental make up of a metallic foil sample (ASand#1 and ASand#2) and the type of a steel alloy (ste23). It was determined that the foil was a sandwich sample of iron and zirconium with the iron side being thinner that the penetration distance of the x-ray. The grade of the steel sample was narrowed down to two from the experimental data. The two grades of steel possible were tool steel S1 and e52100. The steel alloy was determined to be e52100 from the calibrated data that was provided. This determination was made because e52100 has negligible levels of Vanadium, Molybdenum, and Tin well having relative high levels of Chromium and Manganese, and moderate levels of Nickel like the sample had from the calibrated data.

Laboratory 1: XRF Spectroscopy

Ref: Mech 285-0101 Date: 18-Jul-2011

Table of Contents
1 2 Introduction ........................................................................................................... 1 Theory and Experimental Method .......................................................................... 1 2.1 XRF Method .................................................................................................... 1 2.1.1 Experimental Equipment ......................................................................... 1 2.1.2 XRF Measurement Procedure .................................................................. 2 2.2 Identification of a Metal Foil ........................................................................... 3 2.3 Steel Grade Identification ................................................................................ 4 2.4 XRF Radiation sources .................................................................................... 6 Discussion.............................................................................................................. 6 3.1 The Value of XRF ........................................................................................... 7 3.2 Sources of Error............................................................................................... 7 3.3 The Widespread Use of XRF ........................................................................... 7 Conclusions ........................................................................................................... 8 References ............................................................................................................. 8

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Table of Figures
Figure 1 Schematic of a XRF sensor .............................................................................. 2 Figure 2 Count vs. Energy Graph for ASand1 ................................................................ 3 Figure 3 Count vs. Energy Graph for ASand2 ................................................................ 4 Figure 4 Count vs. Energy Graph for ste23 .................................................................... 5

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Laboratory 1: XRF Spectroscopy

Ref: Mech 285-0101 Date: 18-Jul-2011

1 INTRODUCTION
This lab was preformed to introduce the method of X-Ray fluorescence spectroscopy (XRF) and to use XRF to determine the elemental make-ups of different samples. XRF spectroscopy is a method that uses X-rays to cause electrons to excite to be knocked from the inner shells of the atoms to be identified and then the resulting energy radiation that other electrons give off as they do K and L transitions to the lower and more favourable energy shells. The energy given off from these transitions is unique for the different elements so if they are recorded they can be used to identify the elements present in the sample. XRF if a useful technique because it is very accurate (most mistakes are made in interoperating the data collected) and the sample does not have to be destroyed to determine its chemical make-up.

2 THEORY AND EXPERIMENTAL METHOD

This experiment required the use of X-Ray fluorescence spectroscopy to identify the make-up of a sample of foil and the type of steel alloy tested. The XRF device was inspected to give insight into how it operated as its mechanics were explained. 2.1 XRF METHOD X-Ray fluorescence spectroscopy is a method that uses X-rays to cause electrons to excite to be knocked from the inner shells of the atoms of the elements being identified. The resulting radiation that is released by other electrons as they do K and L transitions to the lower and more favourable energy shells is recorded giving a spectroscopy of the sample. The energy given off from these transitions is unique for the different elements so if spectroscopy is analysed it can be used to identify the elements present in the sample. XRF if a useful technique because it is very accurate (most mistakes are made in interoperating the data collected) and the sample does not have to be destroyed to determine their make-up. The spectra produced by the sensor are then compared to the known values for the elements to determine which elements are present in the sample.

2.1.1 EXPERIMENTAL EQUIPMENT The XRF machine used in this experiment is of the older design that is used today. The main difference between the older design and the newer ones is the sensor in the older machines requires to be cooled by liquid nitrogen where as the new ones do not have to be kept as cold. This is not a problem because liquid nitrogen is readily available from the University of Victorias Chemistry department and the sensor in the older machine is more sensitive than the newer ones. The XRF machine is rather small but about half of its size is due to its liquid nitrogen reservoir. The actual measuring apparatus in the
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Laboratory 1: XRF Spectroscopy

Ref: Mech 285-0101 Date: 18-Jul-2011

machine is rather small with two radiation sources held in protective metal casings that slide out when the test is initiated to expose the sample to the X-rays. Some of the Xrays that hit the sample eject the electrons from the sample causing the K and L transitions well other are deflected and picked up by the sensor. These deflected X-rays show up on the spectroscopy the experiment produces and have to be discounted from the results. A schematic of how the X-ray sources and sensor work can be seen in Figure 1.

Figure 1 Schematic of a XRF sensor 2.1.2 XRF MEASUREMENT PROCEDURE To measure a sample using a XRF device the sample must be located in front of the probe. You also have to ensure that there is enough liquid nitrogen in the device to cool the sensor. The device must be connected to a computer through a multi-channel
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Laboratory 1: XRF Spectroscopy

Ref: Mech 285-0101 Date: 18-Jul-2011

analyser. To take the reading the device is switched on and allowed to run for a predetermined amount of time well the sensor collects data. This data is transferred to the computer thought the multi-channel analyser and the count date vs. the Energy is displayed on the screen. Using tables with the known intensities for the different elements the graph is analysed to determine the elements present in the sample and the relative count values is used to determine the percent make up of the sample for each element. 2.2 IDENTIFICATION OF A METAL FOIL The two metal foil sample that was analysed had the side measurements ASand1 and ASand2. The data from these two measurements was used to graph the counts vs. the Energy of the radiation measured. The graph for ASand1 is below in figure 1 and the graph for ASand2 is below in figure 3.

Figure 2 Count vs. Energy Graph for ASand1

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Laboratory 1: XRF Spectroscopy

Ref: Mech 285-0101 Date: 18-Jul-2011

Figure 3 Count vs. Energy Graph for ASand2 The two metals that make up the foil sample that was tested can be determined from these graphs to be Iron (6.40keV) and Zirconium (15.78keV). The composition of the foil sample can be seen to be a sandwich because both elements are not seen equally on the measurements from both sides. The fact that the two metals can be seen from both sides of the sample does not mean that this is an alloy because this is due to the penetration depth of the X-ray source that was used. It can also be determined that the Iron side of the sandwich is relatively thin because the X-ray source was able to penetrate it completely and a good amount to the Zirconium foil which is why the Zirconium count is still higher on the Iron side of the sample. Where as the Zirconium side it thicker with only a little of the X-ray source fully penetrating it into the Iron side. 2.3 STEEL GRADE IDENTIFICATION The steel sample that was examined in this experiment was ste23. The X-ray data that was obtained from this sample is presented in a count vs. energy graph, figure 4 below.

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Laboratory 1: XRF Spectroscopy

Ref: Mech 285-0101 Date: 18-Jul-2011

Figure 4 Count vs. Energy Graph for ste23 This graph shows the different elements that are present in the sample. The peaks that go off of the top of the graph are the peaks associated with the Iron (6.40keV) which is the main component of the sample. In analysing the sample the Iron can be ignored but its effect on the measured values of the other elements near it has to be taken into account. This is done by adjusting the count values for the different elements that fall on the base of the Irons peaks. This can be achieved by comparing the samples measured values with control samples and using the control measurements to normalize the measured values. The radiation source also has to be taken into account in the measuring of the amounts of each element present in the sample. The different radiation sources affect the counts measured for different elements due to the distance the energies of the radiation of the elements are away from the energy of the source. In measuring the steel sample 109Cadmium was used. Using 109Cu causes an over counting of Zirconium and Molybdenum by approximately 3-4 times, Copper and Nickel by 1.5 times and an under counting of Chromium by about 2 times. The values determined from the graph of the sample was that ste23 consisted of trace amounts of Nickel (7.48keV) and reasonable amounts of Magnesium (5.90keV) and Chromium (5.41keV), there were negligible amounts of Vanadium (4.95keV) and Molybdenum (17.48keV) measured and the sample data was cut off before the energy level of Tungsten (59.32keV). These measurements were confirmed by the data given for the calibrated sample outputs. Using the sample measurements and the calibrated data the choice of the steel types was narrowed down to two good possibilities. The possible steel alloys that the sample was determined to be were tool steel S1 or e52100. After scrutinizing
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Laboratory 1: XRF Spectroscopy

Ref: Mech 285-0101 Date: 18-Jul-2011

the calibrated data further it was determines that the best candidate for the steel alloy was e52100 because e52100 in mainly composed of Chromium with relatively high amounts of Magnesium, measurable amounts of nickel and negligible amounts of Vanadium, Molybdenum and Tungsten which is the composition of the calibrated data. These two different spectra analysis techniques (graphing and calibrating) both work well and have their merits the calibration method can give the more accurate results. The calibration method can give more accurate results because it accounts for the effects that the different elements present in the sample can have on each other to give an accurate representation of the chemical make-up of the sample. The graphing technique relies on the skill of the interpreter of the graph to determine the relative composition of the different elements in the sample buy adjusting for the effect that the other elements have on the readings and the effect that the radiation source contributes. The graphical method can be more accurate than the calibration method if the sample being tested does not have a good calibration sample to be tested against. 2.4 XRF RADIATION SOURCES Different sources of radiation are used for XRF measurements. The different sources are used because they produce different energies for their incident beams. It is important to use sources of the appropriate incident beam energy because if the energy of the beam is too much greater than the radiation of the element being examined the readings from that element will not be of the right proportion compared to the other elements in the sample or it might not even be measured. It is also important that the sources radiation is not too close to the samples because this could cause a misreading or even the loss of an element due to the reflected radiation from the source. This reflected radiation could be seen in the data collected for this lab but they were removed from the results. It could be beneficial to use two different radiation sources in taking a XRF measurement. This is because the two sources could allow you to see any elements that would be missed because the element does not produce measurable radiation from one source or covered up by the reflected radiation of the source. Care must be taken if this is done to ensure that the proper composition of the sample is calculated taking into account the different radiation sources would have on the amount of each element measured.

3 DISCUSSION
The method of determining the elemental make-up of unknown samples using X-Ray Fluorescence Spectroscopy was introduced in this lab. Experimentation introduced how the XRF probe worked, how the data was converted to graphs and how the graphs were analysed.

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Laboratory 1: XRF Spectroscopy

Ref: Mech 285-0101 Date: 18-Jul-2011

3.1 THE VALUE OF XRF Using XRF to determine the chemical make up of a sample has many benefits. XRF is a good identification technique because it does not have to destroy the sample being investigated to determine its chemical make up. XRF probes also have been made more and more portable over the last couple of decades which allow for easier use in the field. The XRF technique of analysis is also a relatively fast was of analysing samples. These factors all contribute to XRF being a useful measurement technique for both industry and research. XRF is useful in material sciences because if a compound is found to have desirable properties it can be analysed with XRF to determine its chemical make up. 3.2 SOURCES OF ERROR Even though XRF is a good measurement technique it does have some sources of error associated with it. Elements can be missed from the sample being investigated if they lie with in a peak of another dominate element or with in the foot of the dominate element. This could be seen in the steel identification in the Manganese possibly being hidden in the K peak of the Iron present and in the K peak of the Chromium. The type of radiation source can also effect the results of the experiments with noise introduced due to reflected radiation from the source, the amplitude of the measured values of the elements being dependant on the source used (and how their energies relate). Also elements that are not present could be measured due to the noise present in the data collected. Error can also be introduced in the analysis of the spectra lines produced. These spectra lines must be properly adjusted or they can over or under estimate the measured amounts of the elements present in the sample. The noise in the data can affect the amount of the element counted in the spectra as well as if the counts are not converted properly for the type of radiation used for the source. Even though the calibration model is usually the most accurate way to estimate the chemical make up of a sample the use of calibration models can introduce error to the experimental data. If a good calibration model is not used due to a miscalculation of which should be used or if one is not available the relative amounts of the elements might be misrepresented. 3.3 THE WIDESPREAD USE OF XRF XRF is widely used in research and industry today because it provides very accurate results. XRF is such a chosen method because the probes used for it are small and portable so they can be taken to where the measurements are to be taken, they do not destroy the sample that is being examined unlike chemical processes of identification, and the system is relatively simple to use. XRF is also widely used because the materials required to run them are readily available, newer ones do no even require liquid nitrogen. Most elements can be evaluated using XRF although the sensor can

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Laboratory 1: XRF Spectroscopy

Ref: Mech 285-0101 Date: 18-Jul-2011

have trouble detecting lighter elements. Another limiting factor is that the elements that can be accurately measured depend on the radiation source used. XRF is great for field work because it is compact, accurate and the sample odes not have to be destroyed. There are many possible applications of XRF for the science and engineering of materials. One use would be to analyse two different samples that both exhibit a desirable property to identify the common elements in them so that these common elements can be tested to see if they exhibit the property of what combination of them is required.

4 CONCLUSIONS
XRF spectroscopy is a useful way of measuring the elemental make up of different samples. It was determined that a metal foil sample ASand1 and ASand2) was made up of Iron and Zirconium in a sandwich configuration. The type of steel in a sample (ste23) was also examined and it was determines to be either tool steel S1 of e52100 with e52100 being the most likely of the two.

5 REFERENCES
Department of Mechanical Engineering, MECH 285 Lab 1 XRF Spectroscopy for Elemental Analysis of Materials, May 2010.

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