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Přehled technik – molekulová analýza Reflexní techniky infračervené spektrometrie – ATR,
DRIFT, IRRAS
Infračervená mikrospektroskopie
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Infračervená spektrometrie
ANALYZOVANÉ TYPY MATERIÁLŮ
- plyny - analýza složení zemního plynu
- monitoring vzdušných polutantů
- kapaliny, roztoky - analýza olejů
- analýza odpadních vod
- analýza mléka
- práškové vzorky - analýza léčiv, drog, trhavin
- analýza rud, hnojiv
- fázové rozhraní - povrchová analýza
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Infračervená spektrometrie
- instrumentace
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Infračervená spektrometrie
Oscilující dipólový moment
pohyb molekuly spojený se změnou elektrického
dipolového momentu
vede k absorpci (nebo k emisi) záření
p - aktuální dipólový moment
p0 - dipólový moment v rovnovážné poloze
q - normální souřadnice vibračního módu
ppp
0
0
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Infračervená spektrometrie
Základní výběrové pravidlo
infračervené absorpce
INTENZITA PÁSŮ ÚMĚRNÁ ZMĚNĚ
DIPOLOVÉHO MOMENTU BĚHEM
VIBRAČNÍHO POHYBU
0
q
p
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Infračervená spektrometrie
TYPY VIBRACÍ
• VALENČNÍ – ZMĚNA délky vazby/vazeb
» SYMETRICKÁ
» ANTISYMETRICKÁ
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Infračervená spektrometrie
TYPY VIBRACÍ
• DEFORMAČNÍ - změny úhlů (vazebné úhly,
torsní úhly)
• nůžková, kolébavá, kývavá, kroutivá
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FT-IR reflexní techniky • Infračervený paprsek se odráží od
fázového rozhraní úplným vnitřním
odrazem
• Vzorek musí být v optickém kontaktu
s krystalem
• Snímaná informace z povrchové
vrstvy vzorku
• Pevné látky – prášková forma ,
případně naředěná IČ transparentní
matricí - (KBr)
• Informace z objemu vzorku
• Reflektující vzorek či spíš tenká vrstva
na zrcadlovém podkladu
• Informace z tenké (povrchové)
vrstvy
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Infračervená spektrometrie
- Reflexní techniky
ATR - attenuated total reflection
- zeslabený úplný (vnitřní) odraz
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Infračervená spektrometrie
- Faktory, které ovlivňují ATR spektrální analýzu
POUZE ODRAZ - NIKOLI LOM !
• Vlnová délka infračerveného záření
• Index lomu IRE a vzorku
• Hloubka průniku
• Efektivní délka dráhy
• Úhel dopadu
• Účinnost kontaktu se vzorkem
• Materiál IRE (ATR krystalu)
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Zeslabený totální odraz (ATR)
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Infračervená spektrometrie
ATR - instrumentace
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ATR - instrumentace
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ATR - instrumentace
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SAMPLE ATR element
Circle ATR
Incoming
Light
Exiting
light
Scheme of the Circle ATR Cell
Zeslabený totální odraz (ATR)
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Attenuated Total Reflection (ATR)
ATR Spectra – Ge crystal
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Attenuated Total Reflection (ATR)
ATR Spectra of Rubber – Diamond vs Germanium IRE
Refractive indexes: Ge=4
Diamond=2.4
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Spekulární vs. Difusní Reflexe
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Reflexní techniky
-DRIFT
-rychlé měření práškových vzorků
-- nízká opakovatelnost dat
- složitý fyzikální popis jevu
tvar částic, „zhutnění“ vzorku
index lomu částic
reflektivita a absorpční vlastnosti částic
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Diffuse Reflection
Experimental Setup
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Diffuse Reflection
Experimental Setup – Different Geometry
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Diffuse Reflection
IR Spectra of CaCO3
Ca
CO
3, K
Br ta
ble
ta
Ca
CO
3 v
KB
r, D
RIF
TS
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
Ab
so
rb
an
ce
1000 2000 3000 4000
Wav enumbers (cm-1)
DRIFTs
KBr pellet
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Diffuse Reflection
IR Spectra of 1,2-Bis(diphenyl phosphino)ethane
DRIFTs
KBr pellet
T Armaroli et al. Oil & Gas Science and Technology – Rev. IFP, 59 (2004), 215.
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If the surface is smooth like a mirror:
– reflection and the incidence angles are equal
– reflected beam retains the polarization
characteristics of the incidence beam
Thin layers: 0.5-20 mm angle ~20-60o spectra
similar to transmission ones
Monomolecular layers: angle ~60-85o spectra
predominatly a function of the refractive index
derivative shape of the bands arising from
superposition of extinction coefficient and
dispersion of refractive index
Specular Reflection
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Specular Reflection
Experimental Setup
- selection of incident angle
Incident angle influences
- effective pathlength
- polarized IR response
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K. Yamamoto and H. Ishida, Vibrational Spectrosc., 8, 1 (1994)
Refractive
index
Absorbance
index
Specular Reflection
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Specular Reflection
Correction of „Restrahlen „ bands
IR spektrum bez k orekc e
IR spektrum po ko rekc i pod le Kramerse a Kroniga
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
Ab
so
rb
an
ce
500 1000 1500
Wav enumbers (cm-1)
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Specular Reflection
Correction Kramers-Kronig
Polymethyl methacrylate after KK Transformation
0.2
0.4
0.6
0.8
1.0
Lo
g(1
/R)
Polymethyl methacrylate specular reflectance
4
6
8
10
%T
1000 1500 2000 2500 3000 3500
Wavenumbers (cm-1)
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Nanospectroscopy and microspectroscopy
Chemical images of samples
• Generate from peak heights, areas, peak ratios, correlation, results of principal component analysis etc.
• Useful for monitoring changes in chemical composition in a sample
inhomogeneities, defects, composite materials …
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Nanospectroscopy and microspectroscopy
Chemical images of sample
• Group of points collected over the entire area of interest
Points can be collected in series (mapping – scanning the surface) or in parallel (imaging – multichannel detection)
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Area Mapping and Imaging Group of points collected
over the entire area of interest
Points can be collected in series (mapping) or in parallel (imaging)
Ideal for analysis of highly heterogeneous samples
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Chemical images of sample • IR imaging – multichannel detection
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Chemical images of sample • IR imaging – multichannel detection
PCA selected bands
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Nanospectroscopy vs. microspectroscopy Microspectroscopy –
techniques of far field
• Nanospectroscopy – techniques of near field
• “coupling of a probe
and surface”
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Nanospectroscopy vs. microspectroscopy Microspectroscopy –
techniques of far field
The maximum spatial resolution in a properly designed microscope is limited by the diffraction of light.
• Nanospectroscopy – techniques of near field
• The maximum spatial resolution is under diffraction limit, it is limited mostly by probe aperture (probe diameter).
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Microspectroscopy
Spatial Resolution
the ability to view two closely spaced points as distinct objects
Diffraction
the bending (or “scattering”) of light/energy by an opening of an optical element (lens, aperture)
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Microspectroscopy
Diffraction
the bending of light by an opening of an optical element
occurs when the wavelength of the light approaches the size of the opening
for infrared spectroscopy ~ 10 µm
(1000 cm-1 is 10 µm)
for Raman spectroscopy better than 1 µm
excitation in visible range
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Microspectroscopy
Diffraction
1.22 (6.8 µm)
d = = 6.4 µm
0.58 + 0.71
For 1469 cm -1,
1.22 l
d =
NA obj. + NA cond.
(1469 cm-1 = 6.8 µm )
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Microspectroscopy Diffraction, resolution, sample size
Large sample (>100 μm)
No apparent diffraction
full field
sample area
Small sample (<100 μm)
Diffraction Present
Diffracted radiation
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Microspectroscopy
Minimize Diffraction Effect - Dual Remote Aperture
• First aperture placed between infrared source and sample, limiting IR beam to desired sample area
• Second aperture placed between sample and detector to reduce amount of diffracted light detected
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Microspectroscopy
Minimize Diffraction Effect - Dual Remote Aperture
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IR Microspectroscopy Sampling Modes
Transmission Reflection
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IR Microspectroscopy Sampling Modes
Transmission
Reflection
Secondary mirror
Primary mirror
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IR Microspectroscopy Sampling Modes
Transmission
transparent samples, thin layers
Reflection
ATR
reflection - absorption, specular reflection, grazing angle
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IR Microspectroscopy Sampling Modes
Transmission transparent samples, thin layers
5 - 15 μm thickness
large and uniform surface
mounting in compression cell between windows makes ideal transmission sample
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IR Microspectroscopy Sampling Modes
Reflection - ATR simplifies sample preparation
simplifies sample thickness problem (0.4 - 2.0 μm penetration depth)
position sample on stage
adjust for contact alert – contact sensor
View Mode
IR Mode
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IR Microspectroscopy Sampling Modes
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IR Microspectroscopy Sampling Modes
Reflection - ATR objective crystals - ZnSe, Ge, Si, Diamond
40 μm defect
by Micro ATR Contaminant on Analgesic Tablet
0.00
0.10
0.20
0.30
Lo
g(1
/R)
by Micro ATR Surface of Analgesic Tablet
0.00
0.10
0.20
0.30
Lo
g(1
/R)
1000 1500 2000 2500 3000 3500
Wavenumbers
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IR Microspectroscopy Sampling Modes
Reflection – grazing angle
Collect View
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Polymer Laminate Spectra
50
100
%T
50 %T
50
100
%T
20
%T
1000 1500 2000 2500 3000 3500 4000
Wavenumbers (cm-1)
PET
EVA
PE
Cellulose
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FTIR mikrospektroskopie – příklad
FTIR imaging
microscope
for chemical
composition
and spatial
info at the
cellular scale.
Gives info
like lignin,
starch,
protein and
oil
distribution.
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FTIR mikrospektroskopie – synchrotronové záření
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FTIR mikrospektroskopie – synchrotronové záření
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FTIR mikrospektroskopie – synchrotronové záření
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FTIR mikrospektroskopie – synchrotronové záření
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FTIR mikrospektroskopie – synchrotronové záření
Fig. 5. A) Photomicrograph of pressed fragment of
sample BMM035 from Cave N(a), Bamiyan, showing a
multi-layered structure: 1 = yellowish
transparent layer, 2 = green layer, 3 = black layer, 4 =
white ground, 5 = transparent brownish layer, and
earthen rendering. B) Chemical mappings
obtained by SR-μFTIR, showing the distribution of
three particular ingredients: in red, proteins; in green,
carboxylates; in blue, hydrocerussite.
Map size: 190 × 170 μm2; step size: 10 × 10 μm2. C)
Average FTIR spectra obtained in the green layer (#2),
the white ground layer (#4) and the
transparent brownish layer (#5). The gray rectangles
highlight the vibrational bands used to generate
chemical mappings displayed in B).
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FTIR mikrospektroskopie –srovnání s dalšími metodami
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FTIR mikrospektroskopie –srovnání s dalšími metodami
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SR-FT-IR microspectroscopy spectra (128
scans, 4 cm-1 resolution, spot size 10 µm
10 µm corresponding to (a) linseed drying
oil aged for 7 years; (b) green paint taken
from the altarpiece “El Conestable” from
Jaume Huguet (15th century AD) where a
mixture of bands
related to an aged linseed drying oil and a
metal carboxylate are identified; (c) copper
carboxylate isolated from the green paint
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Fig. 1. Microphotographs of cross-sections corresponding to several samples studied in this work, (a) Kings’ Room in Alhambra from
Granada, (b) Our Lady Santa Ana, (c) El
Salvador Church, (d) Murillo’s painting, (e) Kings’ Room in Alhambra from Granada, and (f) Our Lady Santa Ana.
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Fig. 1. Microphotographs of cross-sections corresponding to several samples studied in this work, (a) Kings’ Room in Alhambra from
Granada, (b) Our Lady Santa Ana, (c) El
Salvador Church, (d) Murillo’s painting, (e) Kings’ Room in Alhambra from Granada, and (f) Our Lady Santa Ana.
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IR Microspectroscopy
Microscopy Applications Small samples
Large Samples
Plastics
Packaging materials
Pharmaceuticals
Fibers
Trace evidence
Contaminants
Failure analysis
Coatings & inks
Electronic materials
Migration, diffusion and aging studies
Reverse engineering
Art conservation
And much more