x-ray Technique Lena Hassan Odeh An- Najah university- N ablus -Palestine

1. x-ray Technique Lena Hassan Odeh An- Najah university- Nablus -Palestine

2. Text • Introduction • Objective. • Discussion: • X-rays and the Production of X-rays • Energy of X-rays • Produce of x-ray • Characteristic X-ray Spectra • X-ray filter • X-ray Diffraction and Bragg's Law • The X-ray Powder Method • References..

3. Introduction: Prior to the discovery of X-rays by Conrad Roentgen in 1895, crystallographers had deduced that crystals are made of an orderly arrangement of atoms and could infer something about this orderly arrangement from measurements of the angles between crystal faces.  The discovery of X-rays gave crystallographers a powerful tool that could "see inside" of crystals and allow for detailed determination of crystal structures and unit cell size. II . Objective: Here we discuss the application of X-rays, not so much in terms of how they are used to determine crystal structure, but how they can be used to identify minerals.   Nevertheless, we still need to know something about X-rays, how they are generated, and how they interact with crystalline solids.

4. electromagnetic spectrum

5. Electromagnetic radiation can be considered as wave motion in accordance with classical theory E = exp (I ω t - Φ) A – amplitude of the wave ω – frequency (ω = 2πν) ϕ – phase (ϕ = ν t) According to the quantum theory electromagnetic radiation can also be considered as a particles called photons. Each photon has associated with it an amount of energy: E=h ν Relationship between wavelength and frequency λ = c/ν

6. I II - X-rays and the Production of X-rays X-rays are electromagnetic radiation with wavelengths between about 0.02 Å and 100 Å).  They are part of the electromagnetic spectrum that includes wavelengths of electromagnetic radiation called visible light. Where Wavelength of visible light ~ 6000 Å. And our eyes are sensitive to (different wavelengths of visible light appear to us as different colors).  Because X-rays have wavelengths similar to the size of atoms, they are useful to explore within crystals.

7. I v - Energy of X-rays

8. Thus, since X-rays have a smaller wavelength than visible light, they have higher energy.  With their higher energy, X-rays can penetrate matter more easily than can visible light.   Their ability to penetrate matter depends on the density of the matter, and thus X-rays provide a powerful tool in medicine for mapping internal structures of the human body (bones have higher density than tissue, and thus are harder for X-rays to penetrate, fractures in bones have a different density than the bone, thus fractures can be seen in X-ray pictures).

9. v. Produce of x-ray • X-rays are produced in a device called an X-ray tube.   It consists of an evacuated chamber with a tungsten filament at one end of the tube, called the cathode, and a metal target at the other end, called an anode.  Electrical current is run through the tungsten filament, causing it to glow and emit electrons.  A large voltage difference (measured in kilovolts) is placed between the cathode and the anode, causing the electrons to move at high velocity from the filament to the anode target.

10. Upon striking the atoms in the target, the electrons dislodge inner shell electrons resulting in outer shell electrons having to jump to a lower energy shell to replace the dislodged electrons.  These electronic transitions results in the generation of  X-rays.  The X-rays then move through a window in the X-ray tube and can be used to provide information on the internal arrangement of atoms in crystals or the structure of internal body parts • Most of the kinetic energy of the electrons striking the target is converted into heat, less than 1% being transformed into x-rays. X-ray tube types: • Gas tube – the original x-ray tube ⇒ obsolete. • Filament tube – most common type of laboratory x-ray source

11. X-ray tube

12. v i. Characteristic X-ray Spectra • When the target material of the X-ray tube is bombarded with electrons accelerated from the cathode filament, two types of X-ray spectra are produced. • The graph shows the relative intensity of x rays emitted at different wavelengths. It can be divided into two parts, a continuous spectrum(the curve) and a line spectrum (the peaks).

13. A typical x ray spectrum is shown below.

14. 1- Continuous Spectrum

15. When a bombarding electron passes close to a nucleus it is deflected (see diagram below). The change of direction means that the electron has been accelerated. An accelerating charged particle emits electro-magnetic radiation. If the acceleration is great enough, the quantum of radiation emitted is an x ray.

16. If an electron passes very close to a nucleus (for example, electron e3 in the diagram) it can be accelerated so much that it gives out all its energy in one quantum. This is therefore the biggest quantum (shortest wavelength) x ray emitted. The minimum wavelength therefore depends on the accelerating voltage. If the accelerating voltage is V, then the kinetic energy possessed by an electron when it reaches the target is e V. Therefore, the minimum wavelength, λmin, is given by target is e V =h c /λ

17. 2- Line or Characteristic Spectrum

18. An electron in the beam can have a collision with an electron in an atom of the target metal. If an electron in a low energy level is excited to a higher energy level, an x ray quantum can be emitted when an electron falls to fill the "space" in the lower energy level.The wavelengths at which the peaks in the spectrum occur thus depend on the material of the target.These "lines" in the spectrum are named after the energy level to which an electron falls, as shown below.

19. This is easiest to see using the simple Bohr model of the atom.  In such a model, the nucleus of the atom containing the protons and neutrons is surrounded by shells of electrons. 

21. The innermost shell, called the K- shell, is surrounded by the L- and M - shells.  When the energy of the electrons accelerated toward the target becomes high enough to dislodge  K- shell electrons, electrons from the L - and M - shells move in to take the place of those dislodged

22. Each of these electronic transitions produces an X-ray with a wavelength that depends on the exact structure of the atom being bombarded. which shown as two sharp peaks in the illustration at left occur when vacancies are produced in the n=1 or K-shell of the atom and electrons drop down from above to fill the gap. The x-rays produced by transitions from the n=2 n=1 levels are called Ka x-rays, and those for the n=3 1 transition are called Kb x-rays. • Transitions to the n=2 or L-shell are designated as L x-rays (n=3 2 is L-alpha, n=4 2 is L-beta, etc. ). The continuous distribution of x-rays which forms the base for the two sharp peaks at left is called "bremsstrahlung" radiation.

23. Bremsstrahlung" means "braking radiation" and is retained from the original German to describe the radiation which is emitted when electrons are decelerated or "braked" when they are fired at a metal target. Accelerated charges give off electromagnetic radiation, and when the energy of the bombarding electrons is high enough, that radiation is in the x-ray region of the electromagnetic spectrum . It is characterized by a continuous distribution of radiation which becomes more intense and shifts toward higher frequencies when the energy of the bombarding electrons is increased.

24. These characteristic X-rays have a much higher intensity than those produced by the continuous spectra, with Ka X-rays having higher intensity than Kb X-rays

25. Characteristic spectra of x-ray

26. v I I . X-ray filter • An X-ray filter is a device to block or filter out some or all wavelengths in the x-ray spectrum. • X-ray filters are used to block low-energy X-rays during medical x-ray imaging (radiography ). • Low energy X-rays are more likely to be absorbed by the patient's soft tissues. This causes non-stochasic radioactive effects, and does not contribute to image quality. • X-ray filters are also used in X-ray crystallography, where crystalline lattice spacing's can be determined using Bragg diffraction. The filters allow only a single X-ray wavelength to penetrate through to a target crystal, allowing the resulting scattering to determine the diffraction distance

27. viii. X-ray Diffraction and Bragg's Law Since a beam of X-rays consists of a bundle of separate waves, the waves can interact with one another.  Such interaction is termed interference

28. If all the waves in the bundle are in phase, that is their crests and troughs occur at exactly the same position (the same as being an integer number of wavelengths out of phase, n λ, n = 1, 2, 3, 4, etc.), the waves will interfere with one another and their amplitudes will add together to produce a resultant wave that is has a higher amplitude (the sum of all the waves that are in phase

30. If the waves are out of phase, being off by a non-integer number of wavelengths, then destructive interference will occur and the amplitude of the waves will be reduced.   the resultant wave will have no amplitude and thus be completely destroyed.

32. Two such X-rays are shown in next slide , where the spacing between the atomic planes occurs over the distance, d.  Ray 1 reflects off of the upper atomic plane at an angle( q) equal to its angle of incidence.  Similarly, Ray 2 reflects off the lower atomic plane at the same angle (q).  While Ray 2 is in the crystal, however, it travels a distance of 2a farther than Ray 1.  If this distance  2a is equal to an integral number of wavelengths (n λ), then Rays  1 and 2 will be in phase on their exit from the crystal and constructive interference will occur.

33. Bragg's Law

34. If the distance  2a is not an integral number of wavelengths, then destructive interference will occur and the waves will not be as strong as when they entered the crystal.  Thus, the condition for constructive interference to occur is n λ = 2a

35. but, from trigonometry, we can figure out what the distance 2a is in terms of the spacing, d, between the atomic planes. a = d sin (q) or 2a = 2 d sin(q) thus, n λ = 2d sin q This is known as Bragg's Lawfor X-ray diffraction.

36. What it says is that if we know the wavelength , λ, of the X-rays going in to the crystal, and we can measure the angle q of the diffracted X-rays coming out of the crystal, then we know the spacing (referred to as d-spacing) between the atomic planes.   • d = n λ /2 sin( q)

37. Again it is important to point out that this diffraction will only occur if the rays are in phase when they emerge, and this will only occur at the appropriate value of n (1, 2, 3, etc.) and q. • In theory, then we could re-orient the crystal so that another atomic plane is exposed and measure the d-spacing between all atomic planes in the crystal, eventually leading us to determine the crystal structure and the size of the unit cell.

38. I x . The X-ray Powder Method In practice, this would be a time consuming operation to reorient the crystal, measure the angle (q), and determine the d-spacing for all atomic planes • A faster way is to use a method called the powder method.  In this method, a mineral is ground up to a fine powder

39. In the powder, are thousands of grains that have random orientations.  With random orientations we might expect most of the different atomic planes to lie parallel to the surface in some of the grains.  Thus, by scanning through an angle q of incident X-ray beams form 0 to 90o, we would expect to find all angles where diffraction has occurred, and each of these angles would be associated with a different atomic spacing.

40. The instrument used to do this is an x-ray powder diffractometer.  It consists of an X-ray tube capable of producing a beam of monochromatic X-rays that can be rotated to produce angles from 0 to 90o.   A powdered mineral sample is placed on a sample stage so that it can be irradiated by the X-ray tube.  To detect the diffracted X-rays, an electronic detector is placed on the other side of the sample from the X-ray tube, and it too is allowed to rotate to produce angles from 0 to 90o

41. diffractometer

42. The instrument used to rotate both the X-ray tube and the detector is called a goniometer.  The goniometer keeps track of the angle q, and sends this information to a computer, while the detector records the rate of X-rays coming out the other side of the sample (in units of counts/sec)  and sends this information to the computer

43. After a scan of the sample the X-ray intensity can be plotted against the angle q (usually reported as 2q because of the way older diffracto meters were made) to produce a chart, like the one shown in next slide .  The angle (2q) for each diffraction peak can then be converted to d-spacing, using the Bragg equation

45. One can then work out the crystal structure and associate each of the diffraction peaks with a different atomic plane in terms of the Miller Index for that plane (h k λ ).

46. EXAMPLE :-Unit Cell Size from Diffraction Data The diffraction pattern of copper metal was measured with x-ray radiation of wavelength of 1.315Å. The first order Bragg diffraction peak was found at an angle 2theta of 50.5 degrees. Calculate the spacing between the diffracting planes in the copper metal. The Bragg equation is n x wavelength = 2dsin(theta) We can rearrange this equation for the unknown spacing d: d = n x wavelength/2sin(theta). theta is 25.25 degrees, n =1, and wavelength = 1.315Å, and therefore d= 1 x 1.315/(2 x 0.4266) = 1.541 Å we will measure the x-ray powder diffraction pattern from a single crystal.. We should measure all the values of 2theta from the chart, and after converting them into d values calculate the repeat distance in your unit cell.

47. Reference: • Joseph Goldstein (2003). Scanning Electron Microscopy and X-Ray Microanalys . Springer. ISBN 978-0-306-47292-3. Retrieved 26 May 2012.  • Joseph Goldstein (2003). Scanning Electron Microscopy and X-Ray Microanalysis. Springer. ISBN 978-0-306-47292-3. Retrieved 26 May 2012 • John M. Cowley (1975) Diffraction physics (North-Holland, Amsterdam) • Pieranski, P (1983). "Colloidal Crystals". Contemporary Physics24: 25