2. الأستاذة الدكتورة/ نجوى فهيم زهران
أهدى هذا العمل المتواضع الى روح
الأستاذة الدكتورة/ نجوى فهيم زهران
فقد كانت المنارة والنبراس لنا و لما لها علينا من ايادى بيضاء فابدا لن ننساكى

3. By Saad Ahmed Abd-Elaal
The Elemental Analysis by Using Non-Destructive Techniques By
Saad Ahmed Abd-Elaal
B.Sc. and M. Sc. In physics
Under the Supervision
Prof. Dr
Ahmed Elfalaky El-sayed
Former Chairman of Physics Department,
Faculty of Science, Zagazig University
Prof. Dr
Abd El-Fatah Ibrahim Helal
Former Vice Chairman of
Atomic Energy Authority
Ass. Prof. Dr.
Hany Talaat Mohsen
Central Lab. for Elemental & Isotopic Analysis, NRC, AEA

4. التحليل العناصرِي باستعمال التقنياتِ اللا إتلافية
رسالة مقدمة من الطالب
سعد أحمد عبد العال
للحصول على درجة الدكتوراة فى الفيزياء
قسم الفيزياء كلية العلوم – جامعة الزقازيق
2011

5. Aim of the work

6. The study the elemental composition and concentrations of some selected Egyptian coins in the last 100 years.
Investigate the probability of amalgamation of some ancient Egyptian coins.
Three different pound coins minted at 2005, 2007 and
2008 are investigated to study the changes of elemental concentration
The possibility of production of nanoparticles from solid samples.
the study the particle size of the ablated particles.

8. SEM-EDX

10. XRF

13. SEM-EDX and XRF are non-destructive and non-invasive analytical techniques.
SEM-EDX and XRF accurate analytical techniques, easy, fast, safe and relatively low cost compared with large facilities.
They are widely used in art, archaeology and ancient historical coins for determination of the material composition.

14. ICP-MS

15. LA Unit

16. Sample Chamber for Laser Ablation Unit

20. Elemental Analysis of some Egyptian Silver Coins in the Ottoman Empire Period

21. ● ●
2,5 and 10 silver Qirsh coins at 1327 AD in the Ottoman Empire period .

22. Qirsh coins elemental analysis by EDX at Ottoman period (mass%)● ●
Qirsh coins elemental analysis by EDX at Ottoman period (mass%)

23. ● ●
LA in the raster mode (a) and in the drilling mode (b) for 10 shots at 7Joules
(a)
(b)

24. LA results of the raster mode elemental analysis of the coins (mass%)● ●
LA results of the raster mode elemental analysis of the coins (mass%)
Element
10 Qirsh
5 Qirsh
2 Qirsh Cu
7.7
7.9 8 Ag
88.8
91.2
91.8 Au
0.68
0.06
0.01 Hg
1.95
0.02
0.03 Tl
0.81
0.29
0.04 Pb --
0.51
0.08

25. ● ●
Variations of silver and mercury concentrations as a function of the depth in micrometers

26. Analysis of some Egyptian coins by using
(XRF)

27. Pt.
67 Year

28. increased Year weight Cu Ni Fe Zn Mn Al 1917 5.6111 75.349 24.0169
0.0676
0.3763
0.1902 -
1938
5.1374
0.2981
0.1078
5.879
0.2982
2.0674
1941
5.1431 --
0.3432
0.1457
1957
4.7843
0.238
0.0741
4.054
1958
4.7675
0.2921
0.0471
4.4568
1960
5.0168
0.2575
0.0549
7.8496
1967
1.799
0.7281
0.0749
0.3546
1973
1.736
0.1186
0.0402
0.6921
0.165
0.6824
3.179
0.2345
0.0508
6.735
1977
3.1641
0.2803
0.037
0.1238
7.6561
1984
1.9741
0.2552
0.0429
7.8952
increased

29. 2 Pt.
1944 – 1984
40 Year

30. Year
weight Cu Ni Fe Al Ag Mn Si
1944
2.6233
0.13
0.1867
0.8746
0.966
0.77
1958
5.586 --
0.0389
8.3816
1980
4.9281
0.2326
5.82
1984
3.2759
0.3003
6.077
increased

31. 5 Pt.
1956 – 2004
48 Year

32. increased Year Cu Ni Fe Zn Mn Co Al Ag 1967 4.4968 74.763 24.936 --
Weight Cu Ni Fe Zn Mn Co Al Ag
1967
4.4968
74.763
24.936 --
0.301
1968
4.5106
0.1123
0.3871
0.1353
0.2176
1969
4.3916
74.47
0.0841
0.3341
0.0846
0.1354
1972
4.4
0.1986
0.5518
0.1411
0.1299
1973
4.4681
0.0824
0.3383
0.0693
0.1082
1974
4.4937
0.6692
0.1171
1975
4.4949
0.3808
0.0612
0.1118
1977
4.4827
0.1226
0.4132
0.262
0.2332
4.4307
0.1048
0.4156
0.2611
1978
4.5644
0.137
0.4557
0.1649
4.4411
0.1283
0.5599
0.2132
1979
4.4898
25.302
0.051
0.5192
0.1542
4.5585
0.122
0.4855
0.1659
1980
4.6312
0.0464
0.3147
0.0829
0.1388
4.4439
74.133
0.1072
0.5086
0.0598
0.1269
1992
3.1613
0.1766
0.0456
6.5119
2004
2.0768
0.231
5.7047
increased

33. 10 Pt.
1960 – 1992
32Year

34. increased Year Cu Ni Fe Zn Mn Co Si Al 1967 5.6605 74.6871 24.3601
Weight Cu Ni Fe Zn Mn Co Si Al
1967
5.6605
0.1987
0.391
0.2375
0.1256 --
5.829
0.0851
0.3258
0.256
0.1561
1970
5.9253
0.0769
0.4821
0.1243
0.135
1971
5.8757
0.1952
0.47
0.1956
0.1405
1972
5.9223
0.207
0.4651
0.1069
0.1322
1974
5.9117
0.3239
0.1836
0.1204
1975
5.6296
0.0712
0.4948
0.1176
0.13
1976
6.0513
0.0757
0.3399
0.1235
1977
6.0375
0.0535
0.3586
0.0625
0.1186
5.9715
0.077
0.4242
0.0849
0.1339
1978
6.0154
73.707
0.1015
0.5661
1979
5.8753
0.055
0.0647
0.1391
6.0348
0.4856
0.2193
0.0932
5.9574
0.4717
0.1471
0.0869
1980
6.0069
0.0572
0.5962
0.0896
0.1159
6.0614
71.628
27.582
0.0601
0.4926
0.1002
0.137
5.9333
0.0586
0.2899
0.1173
0.1638
1984
6.1468
74.617
0.0598
0.3823
0.1304
0.0863
0.4399
1992
4.8997
0.1723
0.0449
0.5114
8.4476
increased

35. Egyptian Pound Coin

36. Ring
Disk

37. Egyptian pound Cu Ni Fe Si Al Mn Zn
2005
Disk
93.23 --
0.36
5.85
0.54
Ring
73.48
24.23
0.32
0.89
2007
76.05
0.29
29.48
0.23
98.42
1.32
2008
0.79
23.16
0.56
94.83
1.78
1.87
Concentration (in mass %) of various elements in one pound Egyptian’s coin by XRF technique

38. disk
ring

39. Egyptian pound Cu Ni Fe Si Al Mn Zn
2005
Disk
surface
91.91 --
0.11
4.95
cross sec.
90.75
0.9
0.69
5.66
0.88
Ring
74.05
24.83
0.31
73.84
25.15
0.07
0.25
2007
64.36
32.64
99.62
0.16
0.14
0.22
99.17
0.83
99.5
0.19
2008
69.34
25.82
99.43
0.13
0.3
0.38
99.56
0.23
0.21
Concentration (in mass %) of various elements in one pound Egyptian’s coin by EDX technique

40. EDX spectra for 2005, 2007 and 2008 coins surfaces and resections.

41. The production of small particles from the pound alloy

42. Nd:YA Glaser lens Ablation cell Ablated material path N2
Deposit material holder
Gas tube
Ablation cell
Sample N2
Nd:YA
Glaser

43. 2μm
1μm
2μm
LA in the raster mode

44. Laser Light Scattering Technique for Determination of Particle Size which Produced by Laser Ablation of Solid Samples

45. Laser: He–Ne Laser =10 mW , =632.8 nm and =612nm .
Principle and setup of LLS technique for measuring the size of small particles
This diagnostic tool is mainly based on Mie scattering technique .
The experimental setup consisted of :
Laser: He–Ne Laser =10 mW , =632.8 nm
and =612nm .
Photomultiplier detector and monochromator.
Oscilloscope: 2 channel oscilloscope with the photomultiplier detector.
Black chamber with beam dumper.

46. Experimental arrangement
Powder size measurement
Ultrasonic powder generator
0- 40 kHz
Beam dumper
monochromator
Isc. 
Black chamber
He-Ne laser
612nm-10mW
Lens
Powder spray
Powder vibrator
Detector
Photon-counting

47. Laser Light Scattering LLS technique
where:
I is the scattered intensity ,
Ii is the incident intensity ,
C is the constant of the experimental setup ,
Np is the particle number density,
/4 is the fraction of the solid angle that reached to the detector ,
a is the particle radius ,
 is the wavelength of the incident laser beam,
l is the distance between the particles and the detector pickup slit and
D(,)2 is dimensionless geometry function. ,
To estimate the ratio of scattering intensity to incident light intensity we use the following formula for the standard material powder ( Light scattering by small particles, by H . C. Van de Hulst Page 109)

48. LLS technique where: I is the scattered intensity ,
To obtain the Np we use Lambert law ,
where:
I is the scattered intensity ,
Ii is the incident intensity ,
Cext is the extinction cross section and Cext  Csct ,
Np is the particle number density and
h is the interaction length,

49. SEM micrograph of standard powder with its size distribution by SEM-PCM.

50. Standard powders with their sizes by SEM-PCM method and the equivalent intensities by LLS technique.

51. (b)
50m
350
(a)
Images of the laser ablation pits produced by the 266nm, 6ns on glass 611 SRM.

52. Laser Ablated Particle Size in Inductively Coupled Plasma Mass Spectrometer

53. Two laser systems are used to focused onto solid samples .
First, Nanosecond Excimer laser with 6ns pulse width, 193nm wavelength , pulse energy 9mJ and pulsed at 200 Hz
Second, Nanosecond Nd:YAG laser with 6ns pulse width, 266nm wavelength , pulse energy 10mJ and pulsed at 200 Hz
Solid geological sample is used as a target sample in the center of the ablation cell

54. SEM photomicrograph of the ablated crater of the 193nm Excimer laser with pulses applied to the sample using 200Hz repetition rate and N2 carrier gas.

56. SEM photomicrograph of the deposit particles on regions II and III
SEM photomicrograph of the deposit particles on regions II and III. (a) Aggregate of deposit particles in region II. (b) Aggregate of deposit particles in region III.

57. SEM photomicrograph of the ablated material of the sample with the regions towards out of the center of outlet tube of the ablation cell. Aggregate of (a) bigger ablated particles. (b) smaller ablated particles.

58. EDX analysis spectra (a), (b) for the geological sample and
EDX analysis spectra (a), (b) for the geological sample and. (c) for the ablated small particles in the bottom of the laser crater.

59. ICP-MS signal intensity for different laser modes with the geological sample.

60. Intensity (Counts/Sec.)
Sample area mode
Drilling mode
SPDR mode
Elements
Intensity (Counts/Sec.) Mn
263.54
105.39
68.43 Fe
294.92 Ni
52.74
15.9
10.1 Zn
1.25
2.76 1 Ga
25.28
6.14
6.77 As
1.9
2.41
1.62 Rb --
9.2
1.03 Se
49.34
64.73
52.14 Y
247.1
133.51
71.74 Ag
1.07
1.19 Ce
1.31
2.65 Gd
1.81 Dy
8.27
1.95
1.35 Eu
1.68
1.97 Er
8.39
3.19
2.04 Yb
2.48
1.22 Pb
6.531
11.32
8.25
ICP-MS signal intensity for the elements of geological sample with different laser modes

61. ● ●
The results of metallographic structure show higher levels of mercury in the surface of the 10-Qirsh silver coins with considerable reduction towards the bulk compared to the silver content. The adding of mercury to the silver coin surface is called AMALGAMATION.

62. (1, 2, 5 and 10) Qirsh coins were the most widely used metal coins in the period of ( ), and this study showed that the analyzed coins give a valuable and important data about the Egyptian economics in that period.
The elemental analysis techniques can be applied to give a real state for the economy of the country.

63. The 2005 pound coin has a high concentration of copper about 90% (mass%) and a minor concentration of aluminum about 6 % (mass %).
The 2007 pound The copper element decreased to 64 % (mass%) and Zn element with a concentration reached to 32% (mass %).
The Microprobe ED analysis showed that the bulk of the coin was different from surface and the alloy was completely iron with a concentration of a value 99.6% from inside and copper exists only on the surface of the coin.
The same was observed in ring of the coin
The 2008 one pound coin was had concentration of 69.3% (mass%) of copper with zinc element with concentration reached to 25.8 % (mass%).

64. Microprobe EDX analysis showed that the bulk of the coin was different from the surface and it had nickel with a concentration of 99.4 % (mass%). The same was observed in ring of the coin where the bulk of the ring was different from the surface and the alloy was completely iron from inside with a concentration of 99.56% (mass%) while the surface of the ring was nickel with a concentration of 99.6% (mass%).
The 2007 coin is iron alloy coated with cooper in case of the disk and coated with nickel in case of the ring coin is nearly the same like 2007 with slight differences in Al and Si.

65. The last part dominates the ability to produce small particles from the coins alloy and solid samples by using laser ablation. These small particles depend on the composition of the alloy.
The LLS is successfully observed the particle size of the ablated materials and coincides with the SEM images of the ablated materials of glass 611.

68. THANKS
GOOD
BAY