X-Ray Scattering on Binary Alloys

Alistair Armstrong-Brown April 28, 2004

Contents
1 Introduction 2 Setup 1 1

Introduction

This report aims to cover all of the basic elements of the X-ray diraction experiment for the 359 Modern Physics Lab, including both the experimental and data analysis aspects. Students should be encouraged to go beyond the suggestions in the manual as the experiment is designed to be open ended. It will be seen, however, that because of the user friendly diractometer, more emphasis must be put on the data analysis side of the investigation in order to do a thorough and in depth report.

Setup

The experiment was performed on the diractometer

Modern Physics Lab 359 X-ray Scattering on Binary Alloys

Alistair Armstrong-Brown January 7, 2005

Contents
1 Introduction 2 Equipment 2.1 Start-up Procedure . . . . . . . . . . . . . . . . . . . . . . . . 2.2 Shutdown Procedure . . . . . . . . . . . . . . . . . . . . . . . 2.3 Mounting the Sample . . . . . . . . . . . . . . . . . . . . . . 3 Software 3.1 Before You Start . . . . . . . 3.2 How to Measure . . . . . . . 3.2.1 Edit DQL . . . . . . . 3.2.2 Job Measurement . . . 3.2.3 Status Display . . . . 3.2.4 Dirac Files Exchange 1 2 2 3 3 4 4 4 5 6 7 7

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

Introduction

This manual aims to initiate you in the use of the diractometer. Care must always be taken when using X-rays as they can be harmful. The diractometer is a powerful yet sensitive tool which does all of the hard work for you. Everything is controlled by the computer linked to the diractometer. There are many stages to go though before you can start to make a measurement, but once the process has been setup there is very little else to be done from an experimental point of view. It is imperative that you are shown how to use the diractometer by someone who has used it before, but all of the setup instructions are listed here in the manual. 1

Equipment

The X-ray diractometer accelerates electrons onto a copper target. These high energy electrons knock out low lying electrons in the inner shell of the Copper target atoms. As the electrons higher up fall down the potential well to ll up the hole, photons are emitted. These photons have wavelengths in the range of a few Angstroms. Electrons from dierent energy levels can ll up the hole, and consequently X-rays of dierent wavelength will be emitted. In order to chose a particular wavelength the X-rays are incident upon a Gobel mirror. This is a concave multi-layered crystal that will diract the beam in a certain direction. As dierent wavelengths are diracted in dierent directions we can establish a monochromatic beam by choosing a crystal with the right plane separation. This beam is passed through two collimating slits, the width of which can be adjusted. In this way a beam of monochromatic radiation can be channelled onto the sample mounting. The X-rays will interact with the sample resulting in diracted rays being emitted in various directions. The detector has another two collimating slits to ensure that the X-rays it detects are from a well dened direction. The more narrow the slits, the sharper the resulting peak, but the lower the number of counts received by the detector. More details of the experimental setup can be found elsewhere in the manual.

2.1

Start-up Procedure

Care must be taken when setting up the diractometer. As stated above X-rays can be harmful, but with proper instruction and a cautious approach there will be no danger to the user. The rst step is to turn on the water ow that cools the element. Both inow and outow valves must be opened. These are located on the wall of the room next door to the diractometer. Turn on the outow before the inow to avoid a buildup of pressure. Next, turn on the power at the grey circuit breaker box behind the diractometer. There are three switches: the High Voltage Supply, the Electronics Control and the Pump. All three of these should be turned on. On the front panel of the diractometer under the Seimens sign is a green switch labelled Mains. Turn this on. Turn the generator key to the I position. Hold down the heater button (which looks like an unhappy face) for ve

seconds. Invariably this causes the green LED to start blinking. If this is indeed the case go to the keyboard and press: shift, X-Ray, 1, enter. Finally press the On button which is located just under the generator key. The X-ray diractometer is now ready to go, it will go to its default settings of 20kV and 5mA. This is the voltage by which the electrons are accelerated onto the target, and the ow of these electrons makes up the current. Both of these can be adjusted for a particular measurement. Care should be taken to always return these settings to their start-up values before the diractometer is turned o. All the diractometer needs now is a sample and instructions from the software.

2.2

Shutdown Procedure

Similarly to start-up the shutdown proceeds as follows: lower current to 5mA, lower voltage to 20kV, Press O, Turn generator key to 0, Turn o green Mains button, Turn o pump at circuit breaker (leave H.V. and electronics on), close valves in next room. Inow then outow.

2.3

Mounting the Sample

The binary alloy samples have been mounted on aluminium plates. These ensure that the top of the sample will be at the right height to encounter the X-ray beam. You, however, are responsible for positioning the sample mount in the x-y plane. There are three spring loaded bolts to hold the 3

sample mount in place. Simply release these springs by pulling on the bolt, and put your sample inside. Try to get the sample in the very center of the exposed region. It is always best to get someone else to show you an ideal sample position. Once you have positioned the sample, release the bolt, allowing the pins to hold the sample. Next, shut the front door. You are now ready to give instructions to the diractometer via the software.

3
3.1

Software
Before You Start

First obtain a login name and password from the administrator: Saverio Biunno. This will allow you to access the network and the computer controlling the diractometer. Next, adjust the environment so that all the data you take will be saved in a desirable location. This can be done by going to the start button on the desktop and going to: Start P rograms SiemensDIF F RACplus D5000#1 environment From this point on the program SiemensDIF F RACplus D5000#1 will be abbreviated to Siemens. In this environment window there are three directories. They are asking where the data is to be sent. The default directories need to be changed to the following ones which have already been created. All of your data will be stored here after each run and can be sent over the network or stored on a oppy disc for later analysis. in in in DF N T $SY ST EM SY ST EM 1 : DF N T $F IL 1 SY ST EM 1 : DF N T $F IL 2 enter enter enter C : \Dif f plus\ C : \DIF F DAT 1\U ser\Data\ C : \DIF F DAT 1\U ser\Data\

When erasing the default entries the program has the irritating habit of inserting a space before your rst letter, make sure this is removed otherwise the program will not be able to store your data. Be sure to add the nal backslash after the path as well.

3.2

How to Measure

There are four steps you have to take in order to take data, which involve four separate programs. It is advisable that you place shortcuts to these 4

four programs on the desktop in the following order for quick access. All of the programs are found in Start P rograms Siemens. 1. Edit DQL, 2. Job Measurement, 3. Status Display, 4. Dirac Files Exchange. The rst program, Edit DQL, is the recipe that the diracometer follows when it takes data. The second, Job Measurement, takes the role of the chef and controls the process. The Status Display does just what it says. It is just a window to check that everything is progressing as planned. The fourth program converts your data into a more universally accepted format. 3.2.1 Edit DQL

Once you open this program it will just display a blank screen. Go to File and chose New. It will next ask what kind of format to use so pick Qualitative Extended. This gives you control over all aspects of the diractometer. There is space for a comment at the start of the DQL, ll this in at you own leisure, it can also be left blank. Scan Type: Choose Locked Coupled so that the sample moves at the same time as the detector. Scan Mode: Choose Step Scan so that the data will be put into bins of nite width. User Task File: Leave this blank. The next section is called Default Scan Parameters and deals with the settings of the sweep, here you can adjust all the parameters you like. Notice that at the end of this section is the calculated sweep time. Play around with the settings until you have a sweep that balances the amount of data you need with the amount of time you have available. Start: The initial angle of the sweep in degrees. The detector cannot be in line with the X-ray beam or it will be damaged by the high intensity so stay above 5 degrees. Note that this is 2. Stop: The nal sweep angle. The detector must not crash into the X-ray tube, so be sure to choose angles below 140 degrees. 5

Step Size: The width of the bins. You can go down to 0.02 degrees. Time per Step: You will need to spend a few seconds at each step to allow the detector to collect counts. Delay time: Enter zero. Scintillation: Set it to One. You can also choose the generator settings here and control the voltage through which the electrons are accelerated, and the current they produce. A setting of 40kV and 30mA is high enough for good readings on these samples. If you would like to change these speak to the technician to check that you will not be overloading anything. Now you have completed the recipe, press ok. You must save it under C : \DIF F DAT 1\U ser\DQLs. 3.2.2 Job Measurement

Be careful as there are two types of program with similar names. JOB Measurement is the correct one and JOB Measurement is not. Once you open the right program a window will open with a table large enough to store several jobs at once. As you only want to do one job per sample it is recommended that your job only consist of one run. You can then start a new job for the next sample. In the rst cell of the column called Raw Filename, enter the name you want your le to have. Next, click on the rst cell in the column named, Parameter File. You will then need to browse for the DQL you have just saved. The program will access this recipe and use it for the scan it is about to perform. Beneath the table are listed the entries you have just made above for the DQL and RAW data le. Check also that the Default Directory has the correct pathway that you should have entered in the environment window. See section (3.1). You must now save the job before you start, save it in C : \DIF F DAT 1\U ser\job. The default name of the job is untitled which may not be a valid lename so use save as and choose an appropriate job name. Sometimes the saving process deletes the raw lename you have just entered and it will need to be entered again. 6

Now press the button labelled Execute Job. You should be prompted to enter the sample at this point. You will then hear the machine rotating and aligning itself to the settings you have chosen for the sweep. A job can be aborted at any time in this program under the Job icon, then Abort Job. You can choose between aborting the job immediately or at the end of your sweep. 3.2.3 Status Display

This is a window which gives the data on screen as it comes in. If you hang around (and if the sample has been aligned correctly) you will slowly see the peaks appear before your very eyes. . . 3.2.4 Dirac Files Exchange

Once the sweep is nished a box will pop-up announcing that the run is over. The Job Measurement window will also display the Job Finished icon. The next thing to do is to adjust the format in which your data can be transported. The software for the diractometer will output a le that is a .RAW extension. The Dirac Files Exchange program converts the .RAW into a .UXD le, which is can be read by Origin or other data analysis programs. It consists of columns of numbers in ASCII format. You need to tell the conversion program how many columns you want the data to be put into, otherwise it will use the default setting of ten columns. Once you have opened the program click on File then UXD Format. A window will appear with all of the settings for the le exchange. Raw Data Format: Check Angle+Intensity Column Width: Check 10. Items per line: 1. Peak List Format: Check Angle+Intensity Field Separator: Normal Also check the Skip Header Information so that all of you les do not start with 30 lines of jargon. Now you can open the le you have just measured. It is found in C : \DIF F DAT 1\U ser\Data. Once the le appears just press the U XD button on the toolbar and you will then be prompted to give the name and path of the new le in ASCII format. You now have your data and the real work can begin.

X-Ray Scattering on Binary Alloys

Alistair Armstrong-Brown February 16, 2004

Contents
1 Introduction 2 Setup 3 Binary Alloys and Lattice Constants 3.1 Results for CuNi . . . . . . . . . . . . . . . . . . . . . . . . . 3.2 Results for PbSn . . . . . . . . . . . . . . . . . . . . . . . . . 4 Calculating Intensities 4.1 Beyond the Structure Factor . . . . . . . . . . . . . . . . . . 4.2 Bad Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3 Tin in Lead . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 2 2 5 6 8 8 12 13

5 Peak Broadening 15 5.1 K1 and K2 . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

Introduction

This report aims to cover all of the basic elements of the X-ray diraction experiment for the 359 Modern Physics Lab, including both the experimental and data analysis aspects. Students should be encouraged to go beyond the suggestions in the manual as the experiment is designed to be open ended. It will be seen, however, that because of the user friendly diractometer, more emphasis must be put on the data analysis side of the investigation in order to do a thorough and in depth report.

Setup

The experiment was performed on the diractometer. Information on the equipment can be found in the manual. The diractometer emits a beam of X-rays with a wavelength of 0.15418 nm by bombarding a copper target with high energy electrons. The samples used were composed of small grains of led down polycrystal, which were then compressed into a manageable size. In this way the orientation of all crystalline axes among every grain of powder is more closely randomised than if a single poly-crystalline sample was used. It turns out that in making a binary alloy there exist correlations between domains of dierent axis orientation. This will manifest itself as peaks of unexpected intensity. The powder diraction method described in the manual explains how the pattern will be equally spread over of cone of angle 2B from the incident beam, where B is the Bragg angle. This pattern will only be uniformly distributed, however, if the grains of the crystal are oriented completely at random (see section 4.2).

Binary Alloys and Lattice Constants

The manual explains possible ways in which a sample can include dierent elements into its lattice. If we assume for the moment that we are only dealing with interstitial substitution (an assumption which we carry through to the end of the report), then introducing a larger element B into a lattice of A will at rst just slightly increase the lattice parameter above that of element A. If the two lattices have the same structure (as is the case for Cu and Ni), then the lattice constant will increase smoothly with increasing foreign element density until the element B dominates the original element and nally you end up with pure element B. Figure 1 shows the data collected for the alloy of Copper and Nickel. Five samples were prepared containing steadily increasing concentrations of Nickel in Copper from 0 to 100%. The position of the peaks can be obtained by tting them to a Gaussian. In the following calculations the error on the peak position is given by 1/8 the width of the peak at half maximum (FWHM) just like the Rayleigh Criterion for resolving peaks. This perhaps unusual choice of error is due to the fact the the tting error will be given by the quality of the entire t with respect to peak area, background counts,

peak position and peak height.

0% Cu 100% Ni 25% Cu 75% Ni 50% Cu 50% Ni 75% Cu 25% Ni 100% Cu 0% Ni

1500

Counts

1000

500

0 40 50 60 70 80 90

2 Theta

Figure 1: Peaks from X-ray diraction on CuNi Alloy. Angle is twice the Bragg angle B . All traces have same scale as shown for pure Cu. = 0.15418nm. Traces have been oset. It is known that both Copper and Nickel have a face centered cubic structure (fcc). Before the lattice constant can be extracted from the data, we need to identify to which Bragg planes the peaks correspond. To do this it is necessary to calculate the structure factor (1) which takes the structure 3

of the basis cell into account:

N

Fhkl =
n=1

fn e2i(hun +kvn +lwn ) ,

(1)

where N is the total number of atoms in the unit cell, fn is the atomic factor (tabulated in terms of sin in appendix 10 of reference [1]) h,k and l are the Miller indices and un , vn , wn are the positions of the atoms within the unit cell. For an fcc lattice there are four atoms located at the origin (0, 0, 0)a and the face centers (1/2, 1/2, 0)a, (1/2, 0, 1/2)a and (0, 1/2, 1/2)a. Putting these into equation (1) shows that not all of the peaks will be present, some of them, like (100), will have an intensity of zero due to destructive interference with other atoms in the basis. In fact it is possible to inspect equation (1) and deduce rules governing which peaks will be absent. For the fcc structure it turns out that Fhkl = 0 if h,k,l have mixed parity 4fn if h,k,l have same parity. (2)

This puts some fairly strict limits on which peaks will be present. Braggs Law (3) then can be applied to the remaining peaks to calculate their position n = d sin , (3)

where d is the distance between scattering planes and is determined by the Miller indices and the lattice constant a 1 h2 + k 2 + l2 = (4) d2 a2 for a cubic lattice. Of course in order to identify the peaks a knowledge of the lattice constant is required, when in fact it was extraction of the lattice constant from the peaks which motivated the peak identication. Thankfully from gure 1 we can deduce that the lattice constant does not shift much from pure Copper (red trace) to pure Nickel (black trace) as the peak positions do not move much. Therefore it is possible to use either tabulated lattice constant to identify the peaks using equation (3). Three peaks are visible in gure 1 corresponding to (111), (200) and (220) in increasing values of . Having identied the peaks we take our known value for wavelength to calculate the lattice constant as a function of concentration. For now 4

we assume that the diractometer has no oset in . This issue will be addressed in section 5.1.

3.1

Results for CuNi

A Gaussian was t to all three peaks in gure 1 for every concentration of the alloy. This gave a value for the peak position and the FWHM. We can then use equation (3) in reverse to give a value for the lattice constant. In fact each peak will give a dierent (but hopefully similar) value for the lattice constant. All the data and a t for lattice constant against concentration is shown in gure 2. The t is a second order polynomial with the coecients displayed in table 1.

Lattice Constant CuNi Alloy

3.62

Lattice Constant [Angstroms]

3.60

3.58

3.56

3.54

(100) (200) (220) Fit

3.52

20

40

60

80

100

Percentage of Copper

Figure 2: Extracted values of the Lattice constant a using a Gaussian t for peaks (100), (200) and (220). Assumed no oset. Error from 1/8 FWHM. It can be seen that the lattice constant does indeed change smoothly with increasing concentration, but that it is not quite a linear relationship. The error in table 1 is generated by the tting program. Another point to mention is that closer inspection of the points in gure 2 show that the (100) in black squares are always lowest and the (220) in green triangles 5

b c d

a = b + cx + dx2 3.52258 +/ 7.24942 104 4 7.57064 10 +/ 4.09167 105 1.4605 106 +/ 3.98489 107

Table 1: Polynomial t of lattice constant to peak position using Braggs Law in gure 1. x is percentage of Copper. always yield higher values of the lattice constant, even though they are consistent within the error bars. This may be due to an oset in the zero angle measured by the diractometer and can be corrected if there are more peaks present, as in the case of Lead or Tin. Because the lattice constant varies smoothly and we do not see any extra peaks in gure 1, we can conclude that we have seen a binary alloy changing from an fcc pure Copper lattice to an fcc pure Nickel lattice without any other phase in between.

3.2

Results for PbSn

Figure 5 shows the data collected for a dierent binary alloy consisting of Tin and Lead. In this alloy things are not a simple as for CuNi. The lattice structure for pure Lead is fcc, the same as Copper and Nickel. This time, however, pure Tin has a tetragonal structure. We expect that intermediate concentrations will show peaks of both an fcc Lead and a tetragonal Tin. It can be seen from a phase diagram of the alloy that they do not dissolve within each other very well (see page 1848 of reference [2]). Therefore dierent domains within the sample, even within each grain in the powder, will be either predominantly fcc Lead or predominantly tetragonal Tin. In fact Lead can take a small percentage of tin inside it, thereby shifting the lattice constant. This is investigated in section 4.3. There is the possibility that a new, entirely dierent phase is encountered at intermediate concentrations. In this case new peaks, not belonging to either of the pure sample diraction patterns should be seen. In fact we do not observe any new peaks in gure 5 at intermediate concentrations and conclude that we get two domains of fcc Lead and tetragonal Tin with varying concentration. Every peak in the alloy samples can be seen to derive from one of the pure traces of either Lead in black or Tin in red. 6

0% Sn 100% Pb 25% Sn 75% Pb 50% Sn 50% Pb 75% Sn 25% Pb 100% Sn 0% Pb

1500

Counts

1000

500

0 0 10 20 30 40 50 60 70 80 90

2 Theta

Figure 3: Lead Tin Alloys Diraction Pattern.

Also very little shifting of the peaks occur, this is another clue that they do not dissolve within each other very well. If they did we would expect that the larger atom would squeeze apart the lattice as it pushed its way inside, increasing the lattice parameter and shifting the peak positions.

4
4.1

Calculating Intensities
Beyond the Structure Factor

Calculation of the structure factor for complicated basis can be a lengthy and tedious process. This then gives a value for the intensity of the radiation scattered from the sample immediately after interacting with the atoms in the sample. It will not, however, represent the measured intensity of the peaks in any experimental setup. Chapter four of reference [1], which also appears in the manual, thoroughly explains all of the factors which need to be taken into account. These factors are: 1. polarisation factor, 2. structure factor F , 3. multiplicity factor p, 4. Lorentz factor, 5. absorption factor, 6. temperature factor. The structure factor has already been mentioned (1) and evaluated for an fcc lattice in equation (2). The polarisation factor accounts for the fact that we are using unpolarised radiation. The multiplicity describes how sometimes many dierent planes will contribute to each peak. For example the (111) peak seen in gure 1 will contain a contribution from the (-1,1,1) and in fact all eight combinations of positive and negative ones. The multiplicity factor is tabulated for all peaks in appendix 11 of reference [1]. The Lorentz factor accounts for all of the geometric factors involved in taking a measurement. One example is how the diractometer sweeps in an arc of a circle around the sample. As mentioned above the X-rays are diracted into a cone of angle 2B from the incident beam. Therefore a circle will intercept a dierent fraction of this cone depending on the scattering angle. The ratio of cosine and sines in equation (5) accounts for the polarisation factor which is the numerator and the Lorentz factor which is the denominator. The absorption factor has not been included in the subsequent calculations for the following reason: it is directly proportional to the volume of the sample irradiated. For small scattering angles the beam does not penetrate the sample very far but the area irradiated is large. Conversely, for 8

Element Pb Cu Ni

B [m2 ] 2.101020 5.301020 4.251021

Table 2: Element coecients for temperature factor. large scattering angles, there is deeper penetration but the irradiation area is smaller. The volume of the sample irradiated remains constant and for calculations of the relative intensity between peaks this term can be omitted. The nal factor covers the thermal vibrations of the atoms in the lattice. The atoms undergo an average displacement of u from their mean position. Two peaks at dierent scattering angles will correspond to dierent plane spacings, d (4). It is the relative displacement u/d which determines the eect on the scattering intensities. In this way an angular dependence creeps into the temperature factor. This is the exponential term in equation (5). All of the factors can be brought together to give the (as yet un-normalised) relative intensity, I, as a function of the scattering angle, , I = |F |2 p 1 + cos2 2 sin2 cos e
2B sin2 2

(5)

where B has been given by Debye as B= x 6h2 T 2 (x) + 4 . mkD (6)

Here T is the sample temperature at measurement in Kelvin, m is the mass of the atom in question, k is Boltzmanns constant and D is the Debye temperature. The function (x) and the Debye temperature can be found in appendix 13 of reference [1], where x is D . Table 2 gives the B T values calculated for the elements in question. Putting in values for all of these factors is best done on a spread sheet, but results for the rst few peaks of Lead are shown in table 3. The peaks are normalised to the highest intensity peak, in this case (111). Data taken to higher scattering angles for Lead is shown in gure 4. The next thing to do is to compare whether the results calculated in table 3 match with those recorded. One of the parameters in the tting process is the area of the Gaussian and should be directly proportional to the total number of counts within the peak. This can be compared to the calculated 9

h 1 2 2 1 2

k 1 0 2 1 2

l 1 0 0 3 2

15.6 18.1 26.1 31.1 32.7

sin 0.27 0.31 0.44 0.52 0.54

2 31.3 36.3 52.3 62.2 65.3

sin

0.17 0.20 0.29 0.33 0.35

fP b 70 67.5 61 57 56

|F |2 78400 72900 59536 51984 50176

p 8 6 12 24 8

Lorz+Pol 24.7 17.9 7.89 5.33 4.79

Temp. 0.88 0.84 0.71 0.62 0.60

I 13 106 6.5 106 4 106 4.1 106 1.1 106

Rel. I 10.0 4.84 2.94 3.05 0.85

Table 3: Relative Intensities for Pb. peak position and relative intensity. Tables (4, 5, 6) compare the calculated relative intensities and area under the measured peaks for Lead, Copper and Nickel respectively.

12000

Data Fit

Counts

6000

0 30 40 50 60 70 80 90 100 110 120 130 140

2 Theta

Figure 4: Data taken up to higher scattering angle for wide slits. Gaussian t of (111) peak is also shown. Lead. Inspection of the nal two columns of tables (4, 5, 6) show that the calculation of the peak position is to within 0.2% of the measured position for all of the pure samples. The intensity, which involves a much more lengthy procedure, in to within 10% for most peaks. The notable exceptions are the (333) peak of Lead and the (220) peaks of both Copper and Nickel. Interestingly both the (244) and (006) fall on the same angle. It is impossible to t two dierently sized Gaussians on the same position, but we notice that the sum of the calculated intensities 0.52 and 0.13 yields 0.65, which is close to the measured intensity of 0.73 for the combined peak. Again within 10%.

10

Peak h k 1 1 2 0 2 2 1 1 2 2 0 0 1 3 2 0 2 2 3 3 0 4 1 3 2 4 0 0

l 1 0 0 3 2 4 3 4 4 3 4 5 4 6

2 31.30 36.30 52.26 62.20 65.30 77.06 85.50 88.29 99.45 108.0 123.5 134.2 138.3 138.3

Calculated Int. Rel. Int. 1.36E7 10.00 6.59E6 4.84 4.00E6 2.94 4.15E6 3.05 1.15E6 0.85 4.52E5 0.33 1.24E6 0.91 1.12E6 0.83 7.93E5 0.58 2.27E5 0.17 3.20E5 0.23 1.34E6 0.99 7.12E5 0.52 1.78E5 0.13

2 31.38 36.38 52.36 62.29 65.38 77.15 85.59 88.36 99.51 108.1 123.6 134.3 138.2 138.2

Measured Area Rel. Area 3980 10.00 1875 4.71 961 2.41 1081 2.72 336 0.84 114 0.29 360 0.90 244 0.61 236 0.59 261 0.66 83 0.21 310 0.78 292 0.73 292 0.73

Measured/Calculated 2 Rel. Intesity 1.00263 0.99965 1.00232 0.97271 1.00173 0.82155 1.00148 0.89093 1.00127 0.99889 1.00114 0.86192 1.00099 0.98944 1.00081 0.74167 1.00061 1.01793 1.00064 3.93161 1.00041 0.88654 1.00025 0.79322 0.99952 1.4038 0.99952 5.61522

Table 4: Comparison of calculated and measured intensities for Pb.

h 1 2 2

Peak k 1 0 2

l 1 0 0

2 43.41 50.57 74.31

Calculated Int. Rel. Int. 351348 10.00 130779 3.722 33481 0.95

2 43.38 50.51 74.22

Measured Area Rel. Area 529 10.00 229 4.33 121 2.29

Measured/Calculated 2 Rel. Intesity 0.9992 0.99949 0.9989 1.1624 0.99876 2.39904

Table 5: Comparison of calculated and measured intensities for Cu.

Peak h k 1 1 2 0 2 2

l 1 0 0

2 44.58 51.95 76.55

Calculated Int. Rel. Int. 312777 10.00 125339 4.01 36337 1.16

2 44.55 51.9 76.45

Measured Area Rel. Area 520 10.00 228 4.31 112 2.12

Measured/Calculated 2 Rel. Intesity 0.99925 0.99951 0.99897 1.07502 0.9987 1.8217

Table 6: Comparison of calculated and measured intensities for Ni.

11

Due to the myriad of terms in equation (5), it is remarkable that the calculated intensities are this close to the measured ones. A job well done.

4.2

Bad Samples

As alluded to earlier, we now turn to the case of an imperfect sample. This was deliberately prepared as a normal piece of everyday lead. This is a polycrystal which will contain domains with dierently oriented crystalline axes. These domains are not, however, randomly oriented. Figure 5 shows data taken from one of these poly-crystalline samples and compares it to a trace taken with a powder sample. As the two samples had dierent monocromating slit congurations their absolute intensities are dierent. They are therefore plotted on dierent scales so that the principal peak is the same size on the gure. In this was we can compare the relative intensities by eye. A more quantitative comparison is also given in table 7.

Powder Sample Polycrystaline

14000 12000 10000 8000 1400 1200 1000 800 600 400 200 0 0 20 40 60 80 100 120 140 160

Counts

6000 4000 2000 0

2 Theta

Figure 5: Comparison between powder and poly-crystalline samples of Lead.

The nal two columns show that the peak positions are again within 0.2% of their predicted values. The intensities, on the other hand, are sometimes 12

h 1 2 2 1 2 0 1 2 2 3 0 1

Peak k 1 0 2 1 2 0 3 0 2 3 4 3

l 1 0 0 3 2 4 3 4 4 3 4 5

2 31.30 36.30 52.27 62.20 65.30 77.06 85.51 88.29 99.45 108.04 123.52 134.25

Calculated Int. Rel. Int. 1.36E7 10.00 6.59E6 4.84 4.00E6 2.94 4.15E6 3.05 1.15E6 0.85 4.52E5 0.33 1.24E6 0.91 1.12E6 0.83 7.93E5 0.58 2.27E5 0.17 3.20E5 0.24 1.33E6 0.98

2 31.29 36.26 52.25 62.15 65.27 77.11 85.44 88.26 99.41 107.97 123.76 134.09

Measured Area Rel. Area 212 10.00 17 0.80 10 0.47 38 1.79 17 0.80 2 0.09 7 0.33 36 1.70 4 0.19 9 0.42 4 0.19 10 0.47

Measured/Calculated 2 Rel. Intesity 0.99975 0.99965 0.99901 0.16557 0.99962 0.16049 0.99923 0.58796 0.99959 0.9488 1.00062 0.28388 0.99924 0.36119 0.99967 2.05432 0.99961 0.3239 0.99935 2.54519 1.00195 0.8021 0.99884 0.48037

Table 7: Comparison of calculated and measured intensities for polycrystalline Lead. only 16% of the calculated value. This shows that there is indeed some correlation in the orientations of the domains in a poly-crystalline sample, and in order to measure the correct intensities the samples must be prepared with care.

4.3

Tin in Lead

As mentioned above, the phase diagram of PbSn shows that Tin is partly soluble in Lead. Lead is fcc with a lattice parameter of 4.95 Angstroms. Tin is tetragonal with lattice constants of 5.63 and 3.18 Angstroms. Tin is a lighter atom than lead and slightly smaller, so we expect that the sample containing 25% Tin will have some domains where some of the lattice points in fcc lead will have been replaced by tin. This will act to reduce the lattice parameter in comparison to pure lead. Because of the increased sweep range of gure 4 it was now possible to try to correct for the instrumental oset at zero angle. The peaks were again all tted with Gaussians, yielding all of the peak positions for dierent values of d. These values, shown in table 8, were then tted to Braggs law (7) using d and as dependant parameters and a and 0 as the tting parameters.

13

Peak h k 1 1 2 0 2 2 1 1 2 2 4 0

l 1 0 0 3 2 0

d 1.73205 2 2.82843 3.31662 3.4641 4

Pure Lead 2 FWHM 31.36 0.14 36.36 0.19 52.33 0.23 62.25 0.30 65.37 0.31 77.09 0.42

25% Tin 75% Lead 2 FWHM 31.37 0.14 36.37 0.18 52.36 0.22 65.39 0.28 77.15 0.29

Table 8: Change in peak positions of Lead with introduction of 25% Tin.

x + 0 . (7) 2a Here, 0 is the oset in the diractometers zero angle. The t of equation (7) is shown in gure 6. = arcsin

1.0 0.8 0.6 0.4 0.2

Theta [rad]

0.0 -0.2 -0.4 -0.6 -0.8 -1.0 -6 -4 -2 0 2 4 6

Data Fit

Lattice Spacings

Figure 6: Fit of equation (7) to 25% Tin 75% Lead. Every peak gave a value for the lattice parameter and the oset, so with enough peaks present it was possible to extract the average and a statistical error for both samples. The results are shown in table 9. The 14

a Oset

Pure Lead 4.9521 +/ 0.0014 0.041 +/ 0.009

25% Tin 75% Lead 4.9485 +/ 0.0007 0.033 +/ 0.004

Table 9: Change in lattice parameter of Lead with introduction of 25% Tin. Theta oset in degrees. lattice parameter does indeed drop to a lower value by about 0.07% which is just outside the error bars. Another thing to note is how small size of the oset. Perhaps this is due to too few peaks being used, or a highly accurate machine.

Peak Broadening

During the tting process the width of each peak is also generated. We now look at how this width varies with scattering angle. Figure 7 shows how the peaks broaden. The black points represent tting a single Gaussian to every peak. In fact most of this broadening is due to peak splitting. The presence of two peaks is due to two very similar, yet dierent, wavelengths being present in the beam. This is discussed in the next section. Fitting these peaks with double Gaussians has been done for the red and blue points in gure 7. As can be seen this signicantly reduces the measured peak width.

5.1

K1 and K2

The nal point to address is the existence of more than one wavelength in the X-ray beam. When the electrons strike the Copper target, low lying bound states are knocked out of the atoms electron shell which are immediately replaced by 2p electrons from higher up. The 2p electrons however come in two types depending on their spin, and there is a small energy dierence between them (Fine structure). The X-rays emitted as these 2p electrons fall down the potential well will have a wavelength inversely proportional to the change in energy. Therefore if we have electrons of two dierent lling up the low lying holes, we will have two slightly dierent wavelengths present. These are the K1 and K2 lines. (In fact many more processes are going on during the electron bombardment of the copper target, but the monochromators will lter out everything else. The K1 and K2 lines, being so close in wavelength, both pass through.)

15

Lead
1.0

Single Peak K a1 K a2

0.8

FWHM [degrees]

0.6

0.4

0.2

20

40

60

80

100

120

140

2 Theta [degrees]

Figure 7: FWHM for peaks in Lead. Peak h k 2 2 3 3 0 4 1 3 2 4 K1 FWHM 0.39 1.54175 0.44 1.54164 0.46 1.54163 0.46 1.54137 0.41 1.54137 K2 FWHM 0.41 1.5454 0.30 1.54632 0.32 1.5456 0.46 1.54522 0.40 1.54489

l 4 3 4 5 4

2 99.43 108.00 123.45 134.10 138.10

+/ 5.56E-4 5.38E-4 4.17E-4 3.28E-4 2.64E-4

2 99.75 108.48 124.00 134.78 138.79

+/ 5.83E-4 3.65E-4 2.87E-4 3.23E-4 2.54E-4

Table 10: Measurement of the two wavelengths from Lead peaks The eect of these two wavelengths will manifest itself as a splitting of the peaks. This may not be visible at low scattering angle as the peaks will be so close together, but at higher angles it is quite clear, see gure 8. It is possible to t a double Gaussian to the data, and extract a dierent wavelength from each peak assuming that we now know the lattice parameter from table 9. This was done for as many peaks as could be resolved see table 10. This gives an average for the two wavelengths and an error given by the average of 1 of the FWHM. This is summarised in table 11. The two values 8 are slightly out from the quoted values found in the manual for the K1 and 16

2000

Counts
0

85

90

95

100

105

110

2 Theta

Figure 8: Peak splitting in Lead at high scattering angle Line K1 K2 1.54155 1.54548 +/ 0.00042 0.00036

Table 11: Extracted values of the two wavelengths from Lead. K2 lines: they are more spaced in reality. This is a little disappointing and could be attributed to poor resolution at these high angle peaks where few counts get through. A smaller sweep range just focussing on the higher angled peaks and taking more counts would probably yield better resolved peaks.

17

References
[1] B.D. Cullity, S.R. Stock, Elements of X-Ray Diraction Third Edition, Prentice Hall (2001). [2] T.B. Massoulsk, B inary Alloy Phas Diagrams, p942 Vol 1 CuNi, p1848 Vol 2 PbSn, American Soc. for Metals.

18