Assessment of Concrete Using

Laser Induced Breakdown

Spectroscopy (LIBS)

Prashant Sunagar
Reg. No : 1MS09CSE11
MTech II Sem
Structural Engineering

1
 Outline
• Introduction (corrosion and significance of its monitoring)
• Principle of LIBS
• Experimental Setup
• Results and Discussions
• Applications of LIBS
• Conclusions

2
Motivation of Concrete Assessment

3
4
5
6
7
 Concrete Evaluation
• The chloride content is an important criterion
for evaluation of the durability of reinforced
concrete (or corrosion occurrence)
• Normal techniques needs chemical laboratory,
a lot of sample preparation, chemicals and are
time consuming so advanced techniques (free
of above mentioned logistics) are worth
investigating for concrete inspection.

8
Advantages of LIBS
 No Sample or little preparation is needed which makes the system
cost effective and less time consuming
 All states of mater can be analyzed, as well as both conductive and
nonconductive samples.
 Very small amount of sample is vaporized

 Capability of remote analysis, in harsh environments.

 Atomization and excitation are in one step.
 Capable of simultaneous multi-element analysis.

 LIBS has a preferably simple set-up, and it is most suitable for

applications in harsh environments, for process control and for on-
site measurements
 Applications of LIBS for the investigation of building materials are
the detection of hydrophobic
9
Principle of LIBS
Atomic emission lines
Laser induced plasma provide species identification
sample

Pulsed laser

Emission Intensity
Fiber optic

Spectrometer Detector

410 415 420 425 430 435 440

10
Wavelength (nm)
Plasma plume

11
 Heating of material
High power
laser pulse Evaporation of material

Focusing lens Dissociation of molecules

Absorption of laser

Plasma plume Plasma ignition

Heating of plasma

Material Plasma expansion

Evolution of laser induced plasma material12

Atomic and molecular transitions at different times
depending on the breakdown thresholds for elements

Ef

E i

13
 26000

22000
intensity (a.u)

18000

14000
0.0μs
0.5μs
10000
1.5μs
6000
2.5μs
2000
430 440 450 460
Wavelength (nm)
Time evolution of the emission spectra of steel sample in the region of 415-445 nm
14
 60000

55000

50000

45000
intensity(a.u)

40000

35000

30000 0.5μs
25000

415 420 425 430 435 440

wavelength(nm)
60000

55000

50000

1.5 μs
45000
intensirty(a.u)

40000

35000

30000

25000

415 420 425 430 435 440

wavelength(nm)

60000

55000

50000

45000
intensity(a.u)

40000

35000 2.5 μs
30000

25000

415 420 425 430 435 440

wavelength (nm)

60000

55000

50000

3.5 μs
45000
intensity (a.u)

40000

35000

30000

25000

415 420 425 430

wavelength (nm)
435 440
15
Experimental setup
 Laser system (1064 nm, 10 Hz)

 Optical detection system

 Synchronization system

 Samples (crude oil, soil, iron slag, ore, plastics,

paint , cement, water etc)
16
 Sample on a
Beam B.S Lens rotary stage
attenuator
Nd:YAG LASER

Oscilloscope

Optical
fiber
Laser
power supply POWER
METER

LIBS 2000
Spectrometer

ICCD

Fig. Schematic diagram of LIBS

17
Setup
Line intensity
When the optical transition occurs between two energy
levels, the intensity of spectral line is given by

hcgAN  E 
I exp   (1)
4  K BT 

18
Quantitative Analysis
Parametric Dependence

Calibration Curves

Limits of Detections

Analysis
19
LIBS Parametric Dependences
and System Calibration

20
 600

Ca(422.8 nm)
550

500

450
Na(588.9 nm)

400 Ca(445.4 nm)

Signal Intensity (arb.unit)

350
Ca(558.6 nm)
Ca(443.9 nm)
300

250 Ca(527.02 nm)

Ca(610.2 nm)
Ca(612.2 nm)
200
K (404.41 nm) Ca(442.5 nm)

150

100

50

0
400 450 500 550 600 650
wave Length (nm)

Typical LIBS Spectra of Calcium in KBr matrix in the region of

400 to 650 nm recorded at delay time of 4.5 µs and laser pulse energy of 25 mJ.
21
 4000 Na (588.99nm)
Mg (518.36 nm)
Mg (517.27nm)
3500

3000 Mg (516.73 nm)

Signal Intensity (arb.unit)

2500

2000

1500

1000 Br (470.4nm)
K (404.41 nm) S (550.97 nm)
500 Mg ii (448.113 nm)

0
400 450 500 550 600 650
Wave Length (nm)

Typical LIBS Spectra of Mg in KBr matrix in the region of 400 to 650 nm

recorded at delay time of 5 µs and laser pulse energy of 25 mJ.
22
 3500
2
R = 0.9965
Ca ( 393.368 nm )
3000

2500

2000
Signal Intensity (arb.u)

1500

1000

500

0
10 15 20 25 30 35
Laser pulse Energy (mJ)
Plot of dependence of the intensity of the Cl 518.36 nm emission
line on laser energy
23
 120

Signal Intensity (arb. units)

60

0
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00
Time Delay (µs)

Fig . Dependence of LIBS signal intensity on the delay time

for trace metal (Cl) present in the oil residue sample.
24
 850

R2 = 0.9975
800

750
Signal Intensity (arb.u)

700

650

600

550

500

450
2 4 6 8 10 12 14
Target Rotator Speed (rpm)

Variation of the intensity of the Cl 518.36 nm emission line

with the target rotation speed.

25
The intensity of a spectral line ‘I’ from an excited atom
or ion in homogenous and optically thin plasma for a
transition from state j --- i is given by:

I = hji Aji N gj Q-1 exp (-Ej /kT)

ji = frequency of the transition from state j --- i

Aji = Einstein coefficient for spontaneous emission
N = population density of ground state
h = Planks constant
Q = Partition function
Ej =energy of upper level

By plotting the intensity versus concentration, one can

detect the unknown concentration from a linear plot for
same element. such plot is called calibration curve
26
 10000

R2 = 0.9996
Signal Intensity (arb.units)

1000

100

10

1
10 100 1000 10000 100000
C once ntration (ppm)
Calibration curve for LIBS measurements of trace metal (magnesium).
The curve was plotted by recording the LIBS signal intensity of the Cl 518.36 nm
emission line at various known concentration in standard samples of magnesium.
27
 Limit of Detection
The detection limit (LOD) can be estimated using
the equation:

LOD = 2b / S

b = the standard deviation of the back ground

S = Sensitivity given by the ratio of the intensity
to the concentration
= Slope of the calibration curve

28
 Limit of Detection of Our LIBS
Setup
Element Wavelength LOD(ppm) Delay (μs)
(nm)
Mg 518.36 9 5
Pb 405.78 7 5.5
Cu 521.82 4 4.5
Ca 422.6 14 5
Fe 404.58 12 4.5
Zn 492.4 5 5
Na 589.5 10 4
Ni 480.66 11 4.5
K 404.41 4 4
Mo 553.56 2 5.5
Cr 425.43 7 5.5
Mn 403.44 6 4.5
P 255.32 4 4.5
S 547.92 7 4.5
Si 250.6 10 4
Sr 460.73 7 4.5
Ti 399.8 10 5
V 440.85 5 4.5
Al 460.98 12 4
Ba 553.54 14 5.5 29
 ANALYSIS OF
CEMENT SAMPLES

30
 LIBS Analysis of Cement Type I Sample

Cement Type I

400
Ca
350
Fe
Signal Intensity (arb.unit)

300 P

250
Ca
Cl
200
Ca
Na
Mg Ca
150

100

50 Cl Al Cr Cl P S
Ca Ba
C S Mn
0 l

200 250 300 350 400 450 500 550 600

Wave Length (nm)

31
 LIBS Analysis of Cement Type V Sample

Cement Type V

160
Fe F
140
Signal Intensity (arb.unit)

120

100
C
P
80 Ca Ca

A Ca Na
60
Mg Ca
40 P
Cr
S C S Ba
Fe Cl
20 Cl Si

0
200 250 300 350 400 450 500 550 600

Wave Length (nm)

32
 LIBS Analysis of Cement Type SF Sample

Cem ent Type SF

600 Na

500
Signal Intensity (arb.Unit)

400

300 Si
Al
Fe Mg

200 Ca
Mg
Cl
Cr
100 Na Si
Si Ba Cl
Al Cl Cr Ba Ca
Al S P

0
200 250 300 350 400 450 500 550 600
Wavelength (nm)

33
Table 1: Elements detected in cement samples and comparison of LIBS Technique with ICP

Elemen Wave Cement Cement Cement LOD Delay

t - Type I Type V Type SF (ppm) (μS)
length LIBS ICP LIBS ICP LIBS ICP
(nm)* (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

Al 394.4 34500 34100 24350 24200 521.4 474 8.0 4.5

Ba 493.4 6280 6080 6731 6620 nd nd 5.0 5.0
Ca 396.1 433500 433000 443480 443000 2090 2043 6.0 5.0

Cr 427.3 96.58 87.8 Nd* Nd* Nd* Nd* 4.0 5.5

Fe 526.9 20230 19300 21980 21200 396 366 7.0 3.5
Mg 518.2 8017 7470 13905 13400 2801 2700 2.0 4.5
Mn 403.4 226.6 206 306.9 279 510.1 475 4.0 4.5
Na 588.9 3211 3010 3977 3680 2852 2760 3.0 3.5
P 438.5 Nd* Nd* Nd* Nd* 825.3 783 7.0 4.5
1
S 373.8 11320 11000 8480 8080 304.7 277 10.0 4.0
1
Si 390.5 92020 88200 81600 81200 351590 349000 11.0 4.5
Cl 585.7 1825 1720 1590 1520 6690.7 6595 12 5.0
*Reference for wavelengths: A. Striganove, and N. Sventitski, Table of Spectral Lines of Neutral
and Ionized Atoms (Plenum New York) 1968 and NIST data base [35]
Nd* : Not detected
34
Comparison of the Results from standard chemical analysis and the results from
LIBS measurements on the cores (Wiggenhauser et al, 2005)
35
Comparison of Glow Discharge Optical Spctroscopy (GD-OES)
with LIBS measurements (Laserna et al 1998))

36
Plasma Plume

Sample

Sample
Holder

(a) Plasma Plume at 25mJ (b) Plasma Plume at 30mJ

(d) Plasma Plume at 40mJ

(c) Plasma Plume at 35mJ

Fig. Images of Laser induced plasma of ore sample at laser

pulse energy of 25,30,35.40 mJ
37
 Table 1: Elements detected in cement samples and comparison of LIBS
Technique with ICP

Element Wave- CementType-1 CementType-5 Cement Type-SF LOD Delay

length (ppm) (μS)
LIBS ICP LIBS ICP LIBS ICP
(nm)*
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

Al 394.4 34500 34100 24350 24200 521.4 474 8.0 4.5

Ba 493.4 6280 6080 6731 6620 nd nd 5.0 5.0
Ca 396.1 433500 433000 443480 443000 2090 2043 6.0 5.0
Cr 427.3 96.58 87.8 Nd* Nd* Nd* Nd* 4.0 5.5
Fe 526.9 20230 19300 21980 21200 396 366 7.0 3.5
Mg 518.2 8017 7470 13905 13400 2801 2700 2.0 4.5
Mn 403.4 226.6 206 306.9 279 510.1 475 4.0 4.5
Na 588.9 3211 3010 3977 3680 2852 2760 3.0 3.5
P 438.51 Nd* Nd* Nd* Nd* 825.3 783 7.0 4.5
S 373.81 11320 11000 8480 8080 304.7 277 10.0 4.0
Si 390.5 92020 88200 81600 81200 351590 349000 11.0 4.5
Cl 585.7 1825 1720 1610 1520 6690.7 6610 12 5.0

*Reference for wavelengths: A. Striganove, and N. Sventitski,

Table of Spectral Lines of Neutral and Ionized Atoms (Plenum New York) 1968 and NIST data base.
Nd*-Not detected 38
 LIBS Remote Sensing

1/23/2018 39
 Other Applications of LIBS
• Pollution monitoring (contaminants in liquids,
solid and gaseous samples).
• Trace element analysis of air, soil and water.
• Immediate determination of ore grades during
mining and prospecting and industrial chemical
process control.
• Chemical analysis of planetary boundary layers
such as Mars etc.
• Chemical analysis of terror agent such as
explosives, strains of anthrax-surrogate bacteria.
40
 Conclusions
• The results achieved in this study show that LIBS
technique is applicable for the detection of chlorine
and other trace elements present in different cement
samples

• The technique holds promise of wider utility because

of its applicability under diverse conditions such as
for the remote analysis or in situ analysis,
microanalysis of small grains (mineral), depth
profiling and multi-elemental analysis.

41
 References
1. Gondal, M. A. T. Hussain (2007), Determination of Poisonous Metals in Waste Water collected from
Paint Manufacturing Plant Using Laser- Induced Breakdown Spectroscopy TALANTA Vol 71, 73-80.
2. Gondal, M. A, T. Hussain, Z. H. Yamani and A.H. Bakry (2007), Determination of Elemental Composition
in Iron Slag Waste Using Laser Induced Breakdown Spectroscopy, J. Environment Science and Health
Vol. 42, No. 6,767-775 (2007).
3. Gondal, M. A. M. N. Siddiqui (2007), Identification of Different Kinds of Plastics Using Laser Induced
Breakdown Spectroscopy for Waste Management, J. Environment Science and Health Part A ,Vol 42,
No13 (2007).
4. Gondal, M. A, T. Hussain, Z. H. Yamani, M. A. Baig (2007), The Role of Various Binding Materials for
Trace Elemental Analysis of Powder Samples Using Laser Induced Breakdown Spectroscopy, Talanta
,Vol 72, 642-649.
5. Gondal, M. A T. Hussain, Z. Ahmad, A. Bakry, (2007), Detection of Contaminants in Ore Samples Using
Laser Induced Break Down Spectroscopy, J. Environment Science and Health Part A Vol. 42, No. 7 ,
879-887 (2007)
6. T. Hussain, M. A. Gondal (2007), Detection of toxic metals in Waste water from Dairy Product Plant
using Laser Induced Breakdown Spectroscopy, Bulletin Of Environmental Contamination & Toxicology
(accepted and in press ).
7. T. Hussain, M. A. Gondal (2007), Monitoring and Assessment of Toxic Metals in gulf war oil spill
contaminated soil using Laser- induced Breakdown Spectroscopy, Environmental Monitoring and
Assessment (on line available on April 6, 2007, 10.1007/s10661-007-9694-2).
8. Gondal, M. A. T. Hussain, and Z. H.Yamani (2007), Parametric investigation of Pellets for Trace Metals
Detection using Laser-Induced Breakdown Spectroscopy, Energy Sources Part A- Environment
(accepted and in press).
9. Gondal, M. A. T. Hussain, Z. H.Yamani and Z. Ahmad (2007), Analysis of Oil, Soil and Ore Samples
using Laser Induced Breakdown Spectroscopy, Bulletin Of Environmental Contamination &
Toxicology, Vol 78, 270-274.
10. T. Hussain, Gondal, M. A. and Z. H.Yamani (2007), Measurement of Nutrients in Green House Soil with
Laser Induced Breakdown Spectroscopy, Environmental Monitoring and Assessment Vol 124, 131-139.
11. Gondal, M. A. T. Hussain, Z. H.Yamani, M.A. Baig (2006), Detection of Heavy Metals in Arabian Crude
Oil Residue using Laser Induced Breakdown Spectroscopy, TALANTA, Vol 69, 1072 .
42
Thank You !

43