4/22/2012 1

Assessment of Concrete Using

Laser Induced Breakdown
Spectroscopy (LIBS)
Dr. M. A. Gondal
Physics Department
4/22/2012 2
Outline
Introduction (corrosion and significance of its monitoring)
Principle of LIBS
Experimental Setup
Results and Discussions
Applications of LIBS
Conclusions
4/22/2012 3
Motivation of Concrete Assessment
4/22/2012 4
4/22/2012 5
4/22/2012 6
4/22/2012 7
4/22/2012 8
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.
4/22/2012 9
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
4/22/2012
10
Laser induced plasma
Principle of LIBS
Fiber optic
Pulsed laser
Atomic emission lines
provide species identification
sample

Detector










Spectrometer


410 415 420 425 430 435 440
Wavelength (nm)
E
m
i
s
s
i
o
n

I
n
t
e
n
s
i
t
y

4/22/2012
11
Plasma plume
4/22/2012
12

Focusing lens
Laser beam
Plasma plume
Regime 1: 1-10 ns Plasma
ignition Thermal and
multiphoton ionization


E
I
E
1
E
K
E
i
E
0

Unspecific
transitions

Some 100 ns
recombination
E
I
E
1
E
K
E
i
E
0


Atomic line
emissions

Some s
relaxations
4/22/2012
13
Material
Heating of material

Evaporation of material

Dissociation of molecules

Absorption of laser

Plasma ignition

Heating of plasma

Plasma expansion
High power
laser pulse
Plasma plume
Focusing lens
Evolution of laser induced plasma material
4/22/2012
14
E
i
E
f
Atomic and molecular transitions at different times
depending on the breakdown thresholds for elements
4/22/2012
15
430 440 450 460
2000
6000
10000
14000
18000
22000
26000
i
n
t
e
n
s
i
t
y

(
a
.
u
)

Wavelength (nm)
1.5s
0.5s
0.0s
2.5s
Time evolution of the emission spectra of steel sample in the region of 415-445 nm

4/22/2012
16
415 420 425 430 435 440
25000
30000
35000
40000
45000
50000
55000
60000


i
n
t
e
n
s
i
t
y
(
a
.
u
)
wavelength(nm)
415 420 425 430 435 440
25000
30000
35000
40000
45000
50000
55000
60000


i
n
t
e
n
s
i
r
t
y
(
a
.
u
)
wavelength(nm)
415 420 425 430 435 440
25000
30000
35000
40000
45000
50000
55000
60000


i
n
t
e
n
s
i
t
y
(
a
.
u
)
wavelength (nm)
415 420 425 430 435 440
25000
30000
35000
40000
45000
50000
55000
60000


i
n
t
e
n
s
i
t
y

(
a
.
u
)
wavelength (nm)



0.5s





1.5 s







2.5 s






3.5 s






4/22/2012
17
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)
4/22/2012
18



Optical fiber







ICCD




LIBS 2000
Spectrometer




POWER
METER
Nd:YAG LASER
Laser
power supply

Beam attenuator



B.S


Lens



Sample on a
rotary stage


Fig. Schematic diagram of LIBS
Setup


Oscilloscope

4/22/2012
19
Line intensity
When the optical transition occurs between two energy
levels, the intensity of spectral line is given by



(1)



|
|
.
|

\
|
=
T K
E hcgAN
I
B
exp
4t
4/22/2012
20
Quantitative Analysis
Parametric Dependence

Calibration Curves

Limits of Detections

Analysis


4/22/2012 21
LIBS Parametric Dependences
and System Calibration

0
50
100
150
200
250
300
350
400
450
500
550
600
400 450 500 550 600 650
wave Length (nm)
S
i
g
n
a
l

I
n
t
e
n
s
i
t
y

(
a
r
b
.
u
n
i
t
)
Ca(442.5 nm)
Ca(443.9 nm)
Ca(445.4 nm)
Ca(422.8 nm)
Na(588.9 nm)
Ca(612.2 nm)
Ca(610.2 nm)
K (404.41 nm)
Ca(527.02 nm)
Ca(558.6 nm)

Typical LIBS Spectra of Calcium in KBr matrix in the region of
400 to 650 nm recorded at delay time of 4.5 s and laser pulse energy of 25 mJ.

0
500
1000
1500
2000
2500
3000
3500
4000
400 450 500 550 600 650
Wave Length (nm)
S
i
g
n
a
l

I
n
t
e
n
s
i
t
y

(
a
r
b
.
u
n
i
t
)
K (404.41 nm)
Mg (518.36 nm)
Mg (517.27nm)
Mg (516.73 nm)
Br (470.4nm)
Mg ii (448.113 nm)
S (550.97 nm)
Na (588.99nm)
Typical LIBS Spectra of Mg in KBr matrix in the region of 400 to 650 nm
recorded at delay time of 5 s and laser pulse energy of 25 mJ.
Ca ( 393.368 nm )
R
2
= 0.9965
0
500
1000
1500
2000
2500
3000
3500
10 15 20 25 30 35
Laser pulse Energy (mJ)
S
i
g
n
a
l

I
n
t
e
n
s
i
t
y

(
a
r
b
.
u
)

Plot of dependence of the intensity of the Mg 518.36 nm emission
line on laser energy
0
60
120
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00
Time Delay (s)
S
i
g
n
a
l

I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)

Fig . Dependence of LIBS signal intensity on the delay time
for trace metal (Zn) present in the oil residue sample.
R
2
= 0.9943
800
900
1000
1100
1200
1300
1400
1500
2000 4000 6000 8000 10000 12000 14000
Pressure Applied (Ib/Sq.In.) for Pellets Formation
S
i
g
n
a
l


I
n
t
e
n
s
i
t
y

(
a
r
b
.
u
)

Dependence of the Emission line intensity of a Mg 518.36 nm line
on the amount of pressure used to make the pellets

0
500
1000
-4 -2 0 2 4 6
Distance from Focal Point for the Focusing Lens (mm)
I
n
t
e
n
s
i
t
y

(
a
r
b

u
n
i
t
s
)

R
2
= 0.9983
200
300
400
500
600
700
800
900
1000
1100
7 9 11 13 15 17 19 21 23 25
Collecting Lens Di stance from Target Surface (mm)
S
i
g
n
a
l

I
n
t
e
n
s
i
t
y

(
a
r
b
.
u
)
Variation of the intensity of the Mg 518.36 nm emission line with the change in the
position of collecting lens from the sample. The maximum signal is recorded at
a distance = 10 mm equal to the focal length of the collecting lens.

R
2
= 0.9975
450
500
550
600
650
700
750
800
850
2 4 6 8 10 12 14
Target Rotator Speed (rpm)
S
i
g
n
a
l

I
n
t
e
n
s
i
t
y

(
a
r
b
.
u
)
Variation of the intensity of the Mg 518.36 nm emission line
with the target rotation speed.
4/22/2012 30
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 = hv
ji
A
ji
N g
j
Q-1 exp (-E
j
/kT)

v
ji
= frequency of the transition from state j ---> i
A
ji
= Einstein coefficient for spontaneous emission
N = population density of ground state
h = Planks constant
Q = Partition function
E
j
=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

R
2
= 0.9996
1
10
100
1000
10000
10 100 1000 10000 100000
Concentrati on (ppm)
S
i
g
n
a
l

I
n
t
e
n
s
i
t
y

(
a
r
b
.
u
n
i
t
s
)
Calibration curve for LIBS measurements of trace metal (magnesium).
The curve was plotted by recording the LIBS signal intensity of the Mg 518.36 nm
emission line at various known concentration in standard samples of magnesium.

Concentration Vs Signal Intensity (Pb)
1
10
100
1000
10000
10 100 1000 10000 100000
Concentration (ppm)
S
i
g
n
a
l

I
n
t
e
n
s
i
t
y

(
a
r
b
.
u
n
i
t
)
Calibration curve for LIBS measurements of trace metal (Pb). The curve was
plotted by recording the LIBS signal intensity of the Pb 405.78 nm emission
line at various known concentration in standard samples of lead.
4/22/2012 33
Limit of Detection
The detection limit (LOD) can be estimated using
the equation:

LOD = 2o
b
/ S

o
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
Limit of Detection of Our LIBS
Setup
Element Wavelength
(nm)
LOD(ppm) Delay (s)
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

4/22/2012 35
LIBS Applications
4/22/2012 36
ANALYSIS OF
CEMENT SAMPLES

LIBS Analysis of Cement Type I Sample
Cement Type I
0
50
100
150
200
250
300
350
400
200 250 300 350 400 450 500 550 600
Wave Length (nm)
S
i
g
n
a
l

I
n
t
e
n
s
i
t
y

(
a
r
b
.
u
n
i
t
)
Cl Al Cr S
Ba
Mg
P
Ca
Ca
Cl
Na
Ca
Ca
Mn
P
Fe
C
l
S
Cl
Ca
LIBS Analysis of Cement Type V Sample
Cement Type V
0
20
40
60
80
100
120
140
160
200 250 300 350 400 450 500 550 600
Wave Length (nm)
S
i
g
n
a
l

I
n
t
e
n
s
i
t
y

(
a
r
b
.
u
n
i
t
)
Fe
Cl
S
A
Ca
C
P
S Ba
Mg
Fe
P
F
C
Ca Ca
Cl
Cr
Ca
Si
Na
Cement Type SF
0
100
200
300
400
500
600
200 250 300 350 400 450 500 550 600
Wavelength (nm)
S
i
g
n
a
l

I
n
t
e
n
s
i
t
y

(
a
r
b
.
U
n
i
t
)
Ca
Na
Mg
Cl Al
Al
Si
Fe
Na
Mg
Si
Ba
Al
Ca
Cl
Cr
Cr Ba
Cl
P S
Si
LIBS Analysis of Cement Type SF Sample
Table 1: Elements detected in cement samples and comparison of LIBS Technique with ICP

Elemen
t
Wave
-
length
(nm)*
Cement
Type I
Cement
Type V
Cement
Type SF
LOD
(ppm)
Delay
(S)
LIBS
(ppm)
ICP
(ppm)
LIBS
(ppm)
ICP
(ppm)
LIBS
(ppm)
ICP
(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
1
Nd* Nd* Nd* Nd* 825.3 783 7.0 4.5
S 373.8
1
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 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
4/22/2012 41
Depth Profiling Using LIBS
Depth Profiling with LIBS for Chloride Content (Wiggenhauser et al, 2005)
Comparison of the Results from standard chemical analysis and the results from
LIBS measurements on the cores (Wiggenhauser et al, 2005)
Comparison of Glow Discharge Optical Spctroscopy (GD-OES)
with LIBS measurements (Laserna et al 1998))
4/22/2012 45
Plasma Plume
Sample
Holder

Sample
(a) Plasma Plume at 25mJ (b) Plasma Plume at 30mJ
(c) Plasma Plume at 35mJ
(d) Plasma Plume at 40mJ
Fig. Images of Laser induced plasma of ore sample at laser
pulse energy of 25,30,35.40 mJ
4/22/2012 46
4/22/2012 47 4/22/2012 47
LIBS Remote Sensing
R
4/22/2012 48
4/22/2012 49
Other LIBS Applications
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.

4/22/2012 50
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
and concrete 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, of
concrete and other metallic structures, depth
profiling and multi-elemental analysis.


Our Publications on LIBS
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 .
Two papers listed in Top 25 Hottest papers
4/22/2012
52
Questions???
Thank You !