1. EBS 325 – Analytical Chemistry Laboratory Introduction To X-Ray Analysis By Mr. Samayamutthirian Palaniandy School of Materials & Mineral Resources Engineering, Engineering Campus, Universiti Sains Malaysia.

2. SAMPLING & SAMPLE PREPARATION XRF XRD

4. SAMPLING SAMPLE PREPARATION

5. or

7. Papers Plastics Glass

8. X-RAY analytical errors Sampling Sample preparation Instrumental Standards Statistical

9. SAMPLE A means by which units are taken from a population in such a way as to represent the characteristics of interest in that population.

10. homogeneous. Well-mixed random accurate representative The equipment does what we want. Our sampling frequency is fine. FAQ about samples and sampling

11. Reasons for poor procedures, equipment, and practices of SAMPLING. Lack of knowledge of the consequences of poor sampling. Lack of knowledge of the sampling theory. Trying to save money.

12. Questions to be answer before sampling WHAT is being sampled? WHY is the sample being taken? WHO is taking the sample? WHERE is the sample taken? WHEN and with what frequency is the sample taken? HOW is the sample taken? HOW MUCH material is in the sample?

13. EXAMPLES OF SAMPLING METHODS Coning & quartering Riffle splitter Paper cone riffle splitter Grab sampling Fractional shoveling

14. CONING AND QUATERING

15. RIFFLE SPLLITING

16. PAPER CONE RIFFLE SPLITTER

17. Fractional Shoveling

18. Grab Sampling Consist of taking a sample using scoop or spatula by simply inserting the sampling device into the sample container and removing an aliquot

19. Sample Mixing Flowing Liquids or Gases A static mixer can reduce the Grouping and Segregation Error. A correct cross stream sample may be impossible to obtain.

20. Precision of Sub-sampling Methods Gerlach, Dobb, Raab, and Nocerino, 2002 Journal of Chemometrics “Gy Sampling in experimental studies. 1. Assessing soil splitting protocols” 16, 321-328

21. Your decisions are only as good as your samples. Your samples are only as good as your sampling systems. Your sampling systems are only as good as your audit and assessment. Summary

22. X-RAY analytical errors Sampling Sample preparation Instrumental Standards Statistical

23. Analytical errors – sampling -Sample must be representative of the process -Sampling must be reproducible (i.e. should be able to take identical duplicate samples)

24. Sample preparation methods must Simple Low cost Rapid Reproducible

25. The quality of sample preparation is at least as important as the quality of the subsequent measurements. Quality of sample preparation

26. An ideal sample would be: -Representative of the material -Homogenous -Of infinite thickness -Without surface irregularities -With small enough particles for the wavelengths being measured

27. SAMPLES METAL POWDERLIQUID XRF only XRD and XRF Why???

28. XRD Working Concept When a monochromatic x-ray beam with wavelength is incident on the lattice planes in a crystal planes in a crystal at an angle , diffraction occurs only when the distance traveled by the rays reflected from successive planes differs by a complete number n of wavelengths. By varying the angle , the Bragg’s Law conditions are satisfied by different d-spacing in polycrystalline materials. Plotting the angular positions and intensities of the resultant diffraction peaks produces a pattern which is characterised of the sample. Where a mixture of different phases is present, the diffractogram is formed by addition of the individual patterns.

29. XRF Working Concept In X-ray fluorescence spectroscopy, the process begins by exposing the sample to a source of x-rays. As these high energy photons strike the sample, they tend to knock electrons out of their orbits around the nuclei of the atoms that make up the sample. When this occurs, an electron from an outer orbit, or “shell”, of the atom will fall into the shell of the missing electron. Since outer shell electrons are more energetic than inner shell electrons, the relocated electron has an excess of energy that is expended as an x-ray fluorescence photon. This fluorescence is unique to the composition of the sample. The detector collects this spectrum and converts them to electrical impulses that are proportional to the energies of the various x-rays in the sample’s spectrum.

30. METAL CHIPSPOLISHINGSOLUTION REMELT CAST BELT GRINDER/ LATHE INGOT LIQUID X-RAY ANALYSIS

31. POWDER GRINDING FUSION SOLUTION PELLET GLASS BEAD LIQUID X-RAY ANALYSIS PRESS

32. LIQUID LIQUID HOLDER DROP METHOD SPOT ANALYSIS DDTC METHOD FILTER X-RAY ANALYSIS

33. Solids Pressed powders Fused beads Liquids Sample types

34. -metal alloys, plastics & glass -relatively easy to prepare by cutting, machining, milling % fine polishing -Avoid smearing of soft metals (e.g. Pb) -Polishing may introduce contamination from the polishing material -do not have particle size problems -Surface needs to be flat -Surface needs to be homogeneous -Surface defects are more critical for light elements if good accuracy is required. Solids

35. -Typical samples types that are prepared as pressed powders include rocks, soil, slag, cements, alumina, fly ash, etc. -Particle size of powder needs to be controlled for light element analysis -If necessary, powders are ground to achieve a particle size of < 50 µm -Grinding can be introduce contamination (e.g. Fe from a chrome steel mill) -Binding agents (e.g. wax or cellulose) can be used to increase sample strength to avoid breakage in the spectrometer -Ground powders are pressed into a solid tablet under pressure using a hydraulic press & 40 mm die -Relatively slow method (≈5 minutes per sample) but relatively low cost -Pressed powders suffer from particle size problems for light elements Preparation equipment needed includes: -Grinding mill and vessel (chrome steel, zirconia, tungsten carbide, etc.) -Hydraulic press and die (usually 40 mm) -Binding agents Pressed powders

36. -Typical samples that are prepared as fused beads include rocks, cements, iron ores, etc. when higher accuracy is required. -Weighed sample is mixed with flux -Sample and flux are melted at ≈ 1000 o C -Melt is poured into a 40 mm mold -Bead surface needs to be homogenous (constant color without cracks) -Slow (10-15 minutes/sample) -High cost -Important benefit is that particle size problems disappear (fusion process results in a homogeneous glass) -An additional benefit is that the melting flux (usually Na or Li borate) dilutes the sample, reducing matrix variations, resulting in higher accuracy -Disadvantage –reduced sensitivity for trace elements Preparation equipment includes: -Fusion device (manual or automatic) -Pt/Au crucible(s) & mould(s) -Fusion (melting) flux -A non wetting agent (e.g. KI or LiBr) is sometimes used to help produce a better quality bead and to assist with cleaning the Pt/Au crucible & mould between samples Fused beads

37. -Typical samples include environmental (waters, mud) & oils -Easiest to prepare -Should have a constant volume that exceeds maximum penetration depth -Sample is poured into a liquid cell fitted with a thin plastic window -Range of window materials to suit different liquids -Fill to a constant height (e.g. 20 mm) to avoid errors from variable depth -Choose the correct thickness and material to suit the chemistry of the sample being measured -Na is lightest element that can be detected in liquids. Liquids

38. Influence of sample preparation

39. Factor of errors in Sample Preparation Grain size and surface roughness Uniformity of sample Contamination through the sample preparation

40. Grain size and surface roughness

41. Uniformity of sample Metallic Sample Casting condition of the sample in the molding. Sand molding Metal molding X-ray intensities differ according to the molding method which comes In the measurement of light elements. Quenching casting which makes the metallic composition fine produces good results Sample polishing NiK  intensityCrK  intensity 50# emery paper0.6860.974 100# emery paper0.6990.983 240# emery paper0.7040.989 Mirror polishing0.7090.993

42. Uniformity of sample Contamination during polishing Contamination effect when carbon steel and Ni-Cr alloy polish after polishing stainless steel. As the contamination form the polishing belt to the sample, the re contamination from The material of the polishing belt and from the remaining trace elements of polished Sample. NiCrFe % Conc0.550.212.10 % Contamination0.050.030.38

43. Powder Sample Grinding Condition Different grinding condition cause variation in particle size distribution which leads to variation in X-Ray intensity.

44. Powder Sample Brequetting Usual forming pressure – 20 tons with 40mm diameter. X-Ray intensities varies with variation of forming pressure (especially when pressure is low). Contamination Contamination from the grinding mill and media

46. CaO,CaCO 3,CaMg(CO 3 ) 2 Ca(OH) 2 etc. If you are given with four bottles of white powder. What will you do to identify them? Identification

47. What is X-ray diffraction? non-destructive analytical technique for identification and quantitative determination of the various crystalline forms, known as ‘phases’. Identification is achieved by comparing the X-ray diffraction pattern

48. Diffractograms and ICDD Card

49. What is X-ray diffraction? XRD able to determine : Which phases are present? At what concentration levels? What are the amorphous content of the sample?

50. How does XRD Works??? Every crystalline substance produce its own XRD pattern, which because it is dependent on the internal structure, is characteristic of that substance. FINGERPRINTThe XRD pattern is often spoken as the “FINGERPRINT” of a mineral or a crystalline substance, because it differs from pattern of every other mineral or crystalline substances.

51. A crystal lattice is a regular three- dimension distribution (cubic, tetragonal, etc.) of atoms in space. These are arrange so that they form a series of parallel planes separated from one another by a distance d, which varies according to the nature of the material. For any crystal planes exist in a number of different orientations- each with its own specific d-spacing Crystal lattice

52. Fourteen (14) Bravais Lattice

53. How does it work? Diffraction Bragg’s Law n =2dsin  When a monochromatic x-ray beam with wavelength is incident on the lattice planes in a crystal planes in a crystal at an angle , diffraction occurs only when the distance traveled by the rays reflected from successive planes differs by a complete number n of wavelengths.

54. How does it work? In powder XRD method, a sample is ground to a powder (±10µm) in order to expose all possible orientations to the X-ray beam of the crystal values of, d and  for diffraction are achieved as follows: 1. is kept constant by using filtered X- radiation that is approximately monochromatic. (See Table 1). 2.d may have value consistent with the crystal structure (See Figure 5). 3.  is the variable parameters, in terms of which the diffraction peaks are measured.

55. Table 1: Monochromatic X-ray filters

56. Basic Component Of XRD Machine Therefore any XRD machine will consist of three basic component. Monochromatic X-ray source ( ) Sample-finely powdered or polished surface-may be rotated against the center – (goniometer). Data collector- such as film, strip chart or magnetic medium/storage. By varying the angle , the Bragg’s Law conditions are satisfied by different d- spacing in polycrystalline materials. Plotting the angular positions and intensities of the resultant diffraction peaks produces a pattern which is characterised of the sample

57. Table 1: Typical experimental XRD data

58. Design and Use of the Indexes for Manual Searching of the PDF Three search methods are used in the indexes – i.e. –The alphabetical index; –The Hanawalt index –The Fink index.

59. The Alphabetical Index

60. Figure 3: Schematic search procedure when chemical information is known

61. Hanawalt Method

62. The Fink Method

63. XRF X-Ray Fluorescence is used to identify and measure the concentration of elements in a sample X-Ray Fluorescence is used to identify and measure the concentration of elements in a sample

64. XRF instrumental parameters x-ray tube kv x-ray tube mA primary beam filters collimator masks x-ray tube kv x-ray tube mA primary beam filters collimator masks collimator crystal detector path collimator crystal detector path

65. user benefits of wavelength dispersive XRF versatile accurate reproducible fast non destructive versatile accurate reproducible fast non destructive

66. XRF is versatile  element range is Be to U atomic numbers (Z) of 4 to 92  concentration range covers 0.1 ppm to 100 %  samples can be in the form of solids, liquids, powders or fragments  element range is Be to U atomic numbers (Z) of 4 to 92  concentration range covers 0.1 ppm to 100 %  samples can be in the form of solids, liquids, powders or fragments

67. XRF is accurate  generally better than 1 % relative (i.e. 10% ± 0.1%)  accuracy is limited by calibration standards, sample preparation, sample matrix, sampling, instrumental errors & statistics  generally better than 1 % relative (i.e. 10% ± 0.1%)  accuracy is limited by calibration standards, sample preparation, sample matrix, sampling, instrumental errors & statistics

68. XRF is reproducible generally within  0.1% relative good reproducibility requires high quality mechanics, stable electronics and careful construction techniques generally within  0.1% relative good reproducibility requires high quality mechanics, stable electronics and careful construction techniques

69. XRF is fast counting times generally between 1 & 50 seconds for each element semi-quant analysis of all matrix elements in 10 to 20 minutes overnight un-attended operation counting times generally between 1 & 50 seconds for each element semi-quant analysis of all matrix elements in 10 to 20 minutes overnight un-attended operation

70. XRF is non-destructive standards are permanent measured samples can be stored and re-analysed at a later date precious samples are not damaged standards are permanent measured samples can be stored and re-analysed at a later date precious samples are not damaged

71. properties of x-rays the following four slides list some of the more important properties of x-rays that contribute to the nature of XRF analysis

72. XRF analytical envelope the following section describes the five major areas that define the analytical possibilities available with wavelength dispersive XRF spectrometers

73. XRF analytical envelope elemental range detection limits analysis times accuracy reproducibility

74. elemental range beryllium (4) to uranium (92) in solids fluorine (9) to uranium (92) in liquids

75. range of elements in solid samples are shown in green (Be to U)

76. range of elements in liquid samples are shown in green (Na to U)

77. detection limits (LLD) function of atomic number (Z) & the mix of elements within the sample (sample matrix) < 1 ppm for high Z in a light matrix (e.g. Pb in petrol) or > 10 ppm for low Z in a heavy matrix (Na in slag)

78. XRF applications summary Na to U in all sample types Be to U in solid samples accuracy generally 0.1 to 1 % relative reproducibility typically < 0.5% relative typical LLD is normally 1 - 10 ppm (depends on element being measured and the sample matrix)

79. XRF errors the following section describes major source of errors in XRF analysis, and investigates how these errors can be minimized to achieve maximize accuracy

80. overview of XRF methodology good accuracy requires careful sample preparation fused beads for light elements accurate standards selection of optimum instrument parameters collection of enough counts to avoid statistical errors

81. Methods of Analysis the following presentation describes the requirements for quantitative and semi-quantitative analysis

82. overview of XRF methodology the objective of XRF is to determine as accurately as possible the composition of unknown samples measured x-ray line intensities are converted to concentrations using an appropriate algorithm

83. overview of XRF methodology each specific application needs to be looked at in detail to determine which method will be the most appropriate

84. XRF analytical methods the atomic number (Z) of each of the elements to be determined will have an influence on the type of sample preparation to be used, and the quantitative or semi-quantitative method that will be the most suitable

85. XRF analytical methods the quantitative method is the most accurate, but requires calibration standards semi-quantitative method is less accurate, but does not require standards the quantitative method is the most accurate, but requires calibration standards semi-quantitative method is less accurate, but does not require standards

86. overview of XRF methodology first determine the following: which elements are to be measured what are their concentration ranges what accuracy is required how many samples are to be measured are suitable standards available

87. overview of XRF methodology elements to be measured low Z will require careful preparation low Z may have lower accuracy low Z may require fusion of powders semi-quant does not measure the very light elements (Be to N)

88. overview of XRF methodology concentration ranges as the concentration range for each element increased, accuracy generally decreases large concentration ranges will require more standards

89. overview of XRF methodology good accuracy requires  careful sample preparation  fusion of powder samples for Z  13  longer analysis time  accurate calibration standards  careful selection of each variable instrument parameter

90. overview of XRF methodology calibration standards require the same sample preparation as unknown samples accurate chemical analysis need to cover concentration ranges mechanically stable

91. XRF applications summary Na to U in all sample types Be to U in solid samples accuracy typically 0.1 to 1 % relative typical LLD is between 1 - 10 ppm

92. semi-quant (standardless analysis) accuracy is limited by  particle size  inhomogeneity  non-measured elements (H to N)

93. semi-quant (standardless analysis) accuracy of the semi-quantitative method can be as good as 1% relative; typically accuracy is between 5% and 10%

94. quantitative analysis calibration graph (x-ray intensity v/s % element) is established for each element that is to be measured measure unknowns using the established calibrations

95. quantitative analysis - calibration for a single element (a), the concentration C is a function f of the intensity I C a = f a x I a

96. quantitative analysis - calibration for multiple elements (a & b) in a sample matrix, the concentration is related to both a & b: C a = f(I a, I b ) or C a = f(I a, C b )

97. quantitative analysis - calibration the object is to obtain the best fit of experimental data to a given algorithm e.g. method of least squares fitting Σ(C chem – C calculated ) 2 = minimum where Σ = sum from all standards and C = concentration

98. quantitative analysis - calibration XRF software typically includes several quantitative methods. The most simplistic method is a straight line calibration where matrix (or inter- element) effects are absent

99. Soalan Pramakmal 1.Nyatakan 5 punca kesalahan analitikal analisis X-Ray. 2.Takrifkan sampel. 3.Apakah punca prosedur pensampelan yang lemah? 4.Nyatakan 5 perkara yang mempengaruhi kualiti penyediaan sampel yang ideal. 5.Terangkan prinsip kerja XRD. 6.Terangkan prinsip kerja XRF. 7.Berikan 5 contoh kaedah pensampelan. 8.Terangkan cara penyediaan “fuse beads”. 9.Nyatakan faktor kesilapan dalam penyediaan sampel yang mempegaruhi analisis X-Ray. 10.Apakah maklumat yang boleh diperolehi daripada keputusan XRD. 11.Tuliskan persamaan Bragg. 12.Nyatakan komponen asas dalam mesin XRD.

100. Soalan Pramakmal 13.Nyatakan 3 kaedah pencarian index unsur dengan manual PDF. 14.Apakah perbezaan kaedah Hanawalt dan Fink? 15.Lakarkan carta alir kaedah Fink. 16.Lakarkan carta alir kaedah Hanawalt. 17.Nyatakan julat no. atom yang boleh dikesan dengan kaedah XRF pada sampel pepejal dan cecair. 18.Apakah kaedah penyediaan sampel yang baik untuk unsur yang mempunyai no. atom yang rendah. 19.Kejituan keputusan XRF dipengaruhi oleh 3 faktor. Nyatakan fator-faktor itu. 20.Apakah itu LOI?