Download - LIBS
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Espectroscopía de descomposición inducida por láser, LIBS
Jesús Anzano Lacarte
Laboratorio LáserUniversidad de Zaragoza
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Objetivo :Objetivo : Desarrollo de una técnica analítica capaz de:Desarrollo de una técnica analítica capaz de:
•Remoto, on-line, análisis “in situ”.
•Simultáneo, anaálisismulti-elemental.
•No- preparación de la muestra.
•Técnica no-invasiva.
•Poca cantidad de muestra.
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InvestigaciónInvestigación•Desarrollo de un instrumento portátil capaz de análisis directo de metales pesados a nivel de ppm.
•Desarrollo de un sistema para análisis on-line de sólidos y slurries.
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Espectroscopía de Emisión AtómicaEspectroscopía de Emisión Atómica
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Laser strikes the surfaceInstant increase in
surface temperature
Vaporization starts, heat dissipates slowly
Underlying layersreach critical T, p
Surface explodes,breakdown occurs,
plasma forms
Plasma expands,becomes opaque,heats environment
Plasma continues expanding,
shock wave forms
Plasma cools down,becomes unstable,
decays
Strong electron-ionrecombination, neutrals form
Plasma productsdiffuse intoenvironment
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• Alta potencia-densidad del pulso láser se focaliza en el material.
• El material ablandado se desarrolla en el plasma caliente.
• Los resultados de emisión a partir del plasma se utilizan para la determinación de los elementos.
• El óptimo de la relación S/N ocurre en un retraso de tiempo específico.
367.15 nm
Pb I
373.99 nm
368.35 nm
363.96 nm357.27 nm
360.00 365.00 370.000
10000
20000
30000
40000
50000
Delay tim
e (s) 8.807.80
6.80
5.804.80
3.802.80
1.80
0.80
Signal counts
Wavelength (nm)
Metodología de LIBS
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kT (eV)
~ Temperature (K)
10 2 10 3 10 4 10 5
103 104 105 106 107 108P
lasm
a D
ensi
ty (
cm-3)
10 2
10 4
10 6
10 8
1010
1012
1022
1024
1020
1018
1016
1014
D
-2
Sun
LIB
HighPressure Arcs
icpThermo-Nuclear Fusion
Fusion expt.
GlowDischarge
Fla
mes
SolarCorona Iono-
sphere
10 0
10 110 010 -110 -2Interstellar
n D3 > 1
Clasificación de Clasificación de los tipos de plasmalos tipos de plasma
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Muestra
HAZ LÁSER (pulsado y focalizado)
reflexión
Introducción
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absorción Muestra
HAZ LÁSER (pulsado y focalizado)
reflexión
Introducción
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absorción Muestra
HAZ LÁSER (pulsado y focalizado)
fragmentaciónfusiónsublimaciónatomización
abs
orc
ión
Introducción
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Muestra
HAZ LÁSER (pulsado y focalizado)
plasma
electronesiones
átomos moléculas
partículas sólidas
abs
orc
ión
Introducción
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Muestra
plasma
Introducción
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Muestra
Introducción
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Muestra
Introducción
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Mínima o nula preparación de la muestra
No se precisa el empleo de reactivos químicos
Análisis simultaneo de varios elementos
Rapidez
Fácilmente automatizable
Resolución espacial
Análisis remoto
Costosa instrumentación
Dificultad para encontrar patrones
Valores altos de %RSD
Efecto matriz
Introducción
VENTAJAS Y DESVENTAJASVENTAJAS Y DESVENTAJAS
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LÁSER
Portamuestras
Selectorespectral
Detector
Plasma
Unidad de control, almacenamiento y procesado de datos
Trigger generador de retrasos
Muestra
Introducción
INSTRUMENTACIÓN LIBSINSTRUMENTACIÓN LIBS
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1.Sistema μ-LIBS
Instrumentación μ-LIBS
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Láser
Espejos dicroicos
ICCD
LenteColectora
EspectrógrafoEchelle
2.LIBS
Instrumentación μ-LIBS
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INSTRUMENTACIÓNINSTRUMENTACIÓN
Muestra 10 m
LÁSERTelescopio Newton
Expansor de haz
Espectrómetro
1.- EXCITACIÓN DEL ANALITO
Tele LIBS.- Experimental
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INSTRUMENTACIÓNINSTRUMENTACIÓN
Plasma 10 m
LÁSERTelescopio Newton
Expansor de haz
Espectrómetro
2.- CAPTACIÓN DE LA SEÑAL DEL PLASMA
Tele LIBS.- Experimental
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Espectrómetro Echelle-ICCD
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Fundamentos de la red de difracción
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Redes Echelle
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iSTAR
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Diseño single window
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Secuencia de lectura de un CCD
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Lectura Vertical Binning
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Horizontal Binning
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Portable LIBS Schematic
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Alloy Paint
Soil
Plasma Imaging
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LIBS - Configuración óptica
Laser
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Detección óptima
252 253 254 255 256 257 258
2
4
6
8
Sig
nal (
coun
ts e
7)
Wavelength (nm)252 253 254 255 256 257 2582
4
6
8
10
12
14
16
Mn
Al
AlP
PP
P
P
P Fe
Fe
FeSi
Si
Sig
nal (
coun
ts e
6)
Wavelength (nm)
Rocas de fosfatos
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Porta LIBS
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Estudios fundamentalesAnálisis cualitativo
• Optimización de la señal.
• Investigación del equilibrio termódinámico del plasma.
• Aumento de la relación S/N.
• Estudio de efectos del tamaño de
partícula
• Mejora en la precisión de muestreo.– Movimiento de la muestra– Energía del pulso del
láser• Investigación de efectos
matríz.– Aluminio, grafito, KBr,
cobre
– NO3, CO3, O, Cl, SO4, S
• Estudios de temperatura del plasma4
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355 360 365 370 375
Tim
e
Pb I373.99 nm
Pb I368.35 nm
Pb I367.15 nm
Pb I363.96 nm
Pb I357.27 nm
Wavelength (nm)
Desarrollo temporal del plasma del plomo
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373.6 373.8 374.0 374.2 374.4 374.6
0.0
2.0x105
4.0x105
6.0x105
8.0x105
1.0x106
1.2x106
1.4x106
Pb I 374 nm line
363.5 364.0 364.5 365.0
0.0
2.0x105
4.0x105
6.0x105
8.0x105
1.0x106
1.2x106
1.4x106
1.6x106
Pb I 364 nm
357.0 357.5 358.0 358.5 359.0
0.0
2.0x105
4.0x105
6.0x105
8.0x105
1.0x106
1.2x106
1.4x106
Pb I 357 nm
0.82 s 1.82 s 2.82 s 3.82 s
Sig
nal (
coun
ts)
Wavelength (nm)
367.0 368.0 369.0 370.0
0.0
2.0x105
4.0x105
6.0x105
8.0x105
1.0x106
1.2x106
1.4x106
1.6x106
1.8x106
2.0x106
Pb I 367 & 368 nm lines
Temporal Development of the Lead LinesTemporal Development of the Lead Lines
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(
(
Tem
pera
ture
(K
)
Height (mm)Delay Time (ns)
Temperature Map of the LIB Lead Plasma
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50 100 150 200 2507600
7800
8000
8200
Tem
pera
ture
(K
)
Pulse Energy (mJ)
0 5 10 15 202000
4000
6000
8000
10000
12000
14000
16000
Tem
pera
ture
(K
)
Time Delay (s)
Temperature in a LIB Plasma
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320 340 360 380 400 420 440 460 480
0
1
2
3
4
Blank Paint
10% Pb in Paint
Pure Pb
Sig
nal (c
ounts
e4)
Wavelength (nm)
395 400 405 410 415
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
Blank Paint
10% Pb in Paint
Pure Pb
Sig
nal (c
ounts
e4)
Wavelength (nm)
Análisis cuantitativoPb en pinturas
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0.0 0.5 1.0 1.5 2.0 2.5
0
200
400
600
800
1000
R2 = 0.98886P
b S
igna
l (co
unts
)
Pb in Paint (w/w %)
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ConclusionsConclusions•Laboratory instrument for “routine” solid analysis.
•Application to various types of matrices
•Minimal sample preparation
•Possibilities of on-line/at-line analysis
•Matrix effects due to the varying sample ablated
•Inter-element effects (only known for zinc)
•Poor precision due to sample heterogeneity
•Standard emission spectroscopy problems
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