Espectroscopia de Infrarrojo por Transformadas de Fourier

Soluciones fuera del Laboratorio con Equipos Porttiles.

Diego Lozada PS, Agilent Technologies. Junio, 27, 2013.

Agenda:

Concepto FT-IR Espectroscopia por Transformadas de Fourier. Nuevo Diseo de Celda de Transmisin para el anlisis de liquidos. Soluciones y Aplicaciones en Espectroscopia de FTIR Mvil. Traer la solucin al problema Resumen.

Qu es la luz infrarrojo?
La luz de Infrarrojo es una regin del Espectro Electromagntico y est despus de la regin visible.
Electric Power

Microwave

Gamma

MID-IR

X-Rays

Visible

4000 400 Frequency in cm-1

El espectro electromagntico esta dividido en regiones especficas incluyendo : Rayos Gamma , Rayos-X, Ultravioleta Visible, Infrarojo Microondas y Radio.

Por conveniencia de las aplicaciones e instrumentatcin, el espectro de infrarrojo es dividido en cercano-, medio-, y lejano infrarrojo. La regin ms comunmente usada es el medio infrarrojo.

Radio

NIR

FIR

UV

Por qu la luz de Infrarrojo puede ser usada?

Energa de infrarrojo es absorbida por una muestra, est causara una exitacin de las vibraciones moleculares de la muestra.

Esta excitacin causa un cambio en la amplitud de los enlaces qumicos. Este cambio es medido en Espectroscopa de Infrarrojo.

Espectro de Infrarrojo
El espectro de infrarrojo de una muestra es una grfica de la cantidad de energa IR (y-axis) que se absorbe a una frecuencia especfica (x-axis) en la regin de IR del espectro electromagntico.
Absorbance

Cada muestra tiene un espectro nico de IR; un espectro de IR puede servir como la huella digital de un compuesto.
4000 3500 3000 2500 2000 1500 1000 500

Wavenumber

(cm-1)

4000

3500

3000

2500

2000

1500

1000

Wavenumbers (cm-1)

Qu beneficios tendra si pudiera llevar su equipo de laboratorio a donde se encuentre su muestra?

Qu es fuera del Laboratorio?

Llevando la instrumentacin del Laboratorio a la muestra.

Acelerar el tiempo de respuesta/resultados: Resultados analticos obtenidos directamente en el sitio Definir estrategia de muestreo Enviar mas muestras relevantes al laboratorio Decidir que reas necesitan mas investigacin

Anlisis no destructivo de muestras grandes: Los objetos no pueden moverse Muy caro que se desarmen

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Diferencias de un instrumento instrumento de Laboratorio

porttil

vs

Similitud entre las necesidades del laboratorio de control de calidad y el anlisis en campo: Misma determinacin realizada una y otra vez, trabajo de rutina. El mtodo puede ser especializado. Usuario final tiende a ser especializado Usualmente un laboratorio porttil es una extensin del laboratorio de control de calidad: El usuario del laboratorio porttil podra no ser un Qumico. Mtodos simples de usar e implementar. Requerimientos instrumentales. similares del anlisis Mismos requerimientos

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Requerimientos de un instrumento porttil:

Caractersticas y especificaciones que resulten en un buen desempeo Que pueda alcanzar los lmites de medicin Buen desempeo Verstil, Robusto, Porttil y Compacto El instrumento debe ir a donde esta la muestra Resistente al uso diario, sujeto a golpes, vibracin y usuarios inexpertos Correcta interface de muestreo Poca o nula preparacin de la muestra Versatilidad: Mltiples usuarios Fcil de usar y que provea de resultados

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NUEVO DISEO DE CELDA DE TRANSMISIN PARA EL ANLIS MUESTRAS LIQUIDAS

DialPath/TumblIR para anlisis de aceites

INOVADOR: Tecnologa revolucionada anlisis de lquidos usando DialPath.

para

Pathlength (m) Typical Conc. Range 30 Neat - 0.1% 50 50% - 500 ppm 100 20% - 100 ppm 200 10 % - 50 ppm

DialPath el nico camino para analizar lquidos!

What matters.. Easy to use so we dont make mistakes DialPath technology gives sealed cell performance with less chance for error

Absorbance Intensity DialPath vs. Sealed Cell 30 m

%T

50 m 100 m 200 m
Toluene 8 second collect

Wavenumber (cm-1)

FT-IR Linea de Productos Agilent

Mobile
Routine
Materials Chemicals
Art Conservation

Analyzers
Routine
Petrochem

Entry
Routine
Chemicals Pharma Academia

Mid-High
Research
Chemicals Petrochem Materials Academia

High
Research
Materials Polymers Academia Bio-Research

Biodiesel

Soluciones Mviles a travs de Sistemas Porttiles.

Agilent Confidential

Posicionamiento Portafolio FT-IR Agilent

Analizadores para Mediciones Mviles.
Dedicated Analyzer Chem/Petrochem Sealed unit with fixed sampling interface with method-driven software Customers wanting to do measurements in a nonlab environment and measuring samples based on standard or inhouse methods, eg. measuring Biodiesel or Oil Analysis Out-of-lab Materials testing, Chemicals Interchangeable sampling accessories Customers that require flexibility to take the instrument to the sample, where the sample cannot be easily prepared for traditional lab-based FTIR measurements

5500 Series FTIR

4100 Exoscan

4500 Series FTIR

Portable Analyzer Chemicals, Petrochem Fixed sampling interface with method-driven software Customers needing remote capabilities but still doing specific applications eg. oil in wind turbines

Out-of-lab Materials testing, Chemicals Customers needing added flexibility getting to hard-toreach areas where the handheld Exoscan cannot

4200 Flexscan

Agilent Confidential

Soluciones para Control Analtico y Control de Calidad.

630 ptica

Dialpath

TumblIR

Reflectancia Difusa

Transmisin

ATR de Diamante
Agilent Confidential

Nuevos accesorios:
Expandiendo nuestro alcance

10 Degree Spec

630 Engine

5B (Bounce) ZnSe ATR

45 Degree Spec
18

1B Ge ATR
Agilent Confidential

Posicionamiento Portafolio FT-IR Agilent

En-laboratoriopara rutina a investigacin
Routine Chemicals, Pharma/Biotech, Academic teaching Customers doing routine FTIR measurements in the MidIR spectral region Customers whose budget is <$20K Majority of 640 FTIR customers will fit the profile for a 630 FTIR Research Materials/Polymers, Chemicals, Biotech, Academic research Customers needing superior optical performance Customers wanting to perform high-end experiments: PEM-IRRAS, PAS, us and ns TRS

630 FTIR

670/680 FTIR

660 FTIR

Routine-Research Materials/Polymers, Chemicals, Biotech, Academic research Customers needing more than MidIR or DTGS capabilities Customers who want to expand their capabilities in the future

Research Materials/Polymers, Chemicals, Biotech, Academic research Customers needing to measure <10um in area Customers wanting to do imaging, primarily looking at small defects within a larger sample.

610/620 FTIR

Agilent Confidential

Aplicaciones FTIR

Aplicaciones FTIR!

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July 8, 2013

Monitoreo de degradacin de aceite por FT-IR

Oxidacin
Sulfatacin Nitracin Holln Agua Glicol Inhibidores de fenol

ZDDP

(inhibidor de oxidacin y corrosin) Zinc

Dialkil Ditiofosfato

Soluciones Agilent dedicadas para el Monitoreo de degradacin : FT-IR 4500t/ 5500t

Los sisteman cuentan con las msmas especificaciones . Solo trabajan en el intervalo MIR (4000 400 cm-1). El sistema Porttil 4500 FT-IR opera con baterias para usarse en sitio de muestreo. Software idntico. El 4500 FTIR es un sistema portatil para su transporte.

Soluciones Agilent dedicadas para el Monitoreo de degradacin : FT-IR 4500t/ 5500t

Son excelentes herramientas para el anlisis de muestras en fase lquida. Podemos Identificar el material ID de Materiales.

Cuantificacin Cuantificacin simple.

El 5500 es fcil de mover y puede ser usado en una mesa o en un Laboratorio mvil. El 5500 es el FTIR ms pequeo del mercado. USO DE CONTROLADOR PDA para el modelo 4500.

Identificacin Propylene Glycol Triacetin

Mtodos simples de cuantificacin: Pasa o no pasa con indicacin de color rojo o verde en pantalla.

Real World Applications

Hydrocarbon Contamination in Soil

Composite Evaluation for High Performance Sailboats

Ziltek, Australia www.Ziltek.com.au

QI Composites,Italy www.QIcomposites.com

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Todays Overview of Applications

Material and Engineering
Solar panels & Aerospatial (composite, heat damage, curing) Elastomers Identification

Energy and Lubricant

Lubricant ID, lifetime (condition) Biodiesel and fuel quality

Food Stuff Identification and Adulteration

Birds nest Edible oil

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Coatings, Films and Surfaces Applications by Handhed FTIR

Evaluation of Curing Process
Effectiveness of curing agent Solvent residue after curing process Detect hardener in curing process Evaluate polyurethane curing on metal
Thermal and UV degradation of composites PVC analysis on steel

QA/QC of materials and surfaces

Pass/fail analysis of epoxy on steel Identify special coatings on aluminum

Primers
Effectiveness of adhesive bonding primer as a function of ambient conditions Measure primer thickness on aluminum Primer adherence on damaged composite

Contamination analysis
Effect of silicone and hydrocarbon oil on bonding

Aging of Composite/Plastics
Oxidation of polyurethane paint

General Epoxy Resin & Hardener reaction

Hardener Epoxy Resin

A commercial system contains a variety of Epoxides each for a specfiic purpose as well as a variety of differing aminic groups and potentially other additives

Epoxy Polymer

End Cure Detection/ Unfinished Cure

Increasing with time

30 C cure, spectra collected at 30 min intervals

Surface Damage
Oxidation of Carbon Composite
Aircraft and other structures will increasingly be constructed from composite material

Composites Serve as Primary Structural Material

787-8

Carbon laminate

Composites are susceptible to heat and oxidative damage Chemical damage of the epoxy resin Exoscan provides new type of non destructive testing to detect heat damage

Carbon sandwich Other composites Aluminum Titanium

Other Steel 5% 10% CFRP Titanium 15%

43%

Misc. 9%

Composites 50%

Aluminum 20%

0.14

0.12

0.1
Absorbance

Exoscan specified in Boeing 787 NDT Manual

0.08

High damage

0.06

0.04

0.02

0 2000 1900 1800

No damage
1700 1600 1500 Wavenumber 1400 1300 1200

(proposed)

Absorbance

OH

OH

O
O
0.14

S O

0.12

0.1

High damage

0.08

0.06

0.04

0.02

No damage

0 2000 1900 1800 1700 1600 1500 Wavenumber 1400 1300 1200

Thermal Damage Study Changes in FTIR Spectra 1310 cm-1 1340 cm-1 Epoxy O O

S OH O

Thermal Damage Study Changes in FTIR Spectra Imide BMI Resin Cyclic (1730 cm-1) not heated
Opened ring (1745 cm-1) heated P-aromatic (Not heated) C-N-C (?) (Not heated)

O=C=N-Ph (heated)

00AV (not Heated) vs. 17AV (Heated)

Flexscan Integrated with US-50

Approximate Measurement Area

A part program was written to map the heat damage over a small area of the part. The program contained a grid pattern. At each location in the grid the instrument was held normal to the part surface for measurement.
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Heat Damage

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Specialized Coatings - Anodized and Coated Aluminium Specular Reflectance

Highly polished, anodized then subsequently coated (with a variety of coatings) aluminium high reflectivity reflectors. Samples ran with the 45 Specular Reflectance interface - 4100 ExoScan FTIR.

Oxide Thickness using Grazing Angle: sub-micron

The Grazing Angle sampling head is closely related to the External Reflectance 45 sampling head

45 80

and/or oxide and/or coating

Oxide Thickness using Grazing Angle: sub-micron

front 00_2009-05-08t17-12-10(1)
0.14 0.12 0.10 0.08 0.06 0.04 0.02 0.00 -0.02
1264.0 1187.7 925.2 908.7

0.16

Al-oxide
Metal Oxide Peak 1

1 m

Metal Oxide Peak 2

Absorbance

~15 second LOD ~25 nm oxide thickness

0.5 m

-0.04 -0.06 -0.08 1500 1450 1400 1350 1300

50 nm
1110.9

Blank
1250 1200 1150 1100 1050 Wavenumber 1000 950 900 850 800 750 700

Specialized Coatings - Anodized and Coated Aluminium Specular Reflectance

Distinct spectra with variation due to thickness of the coating under examination Silicone based coating Acryl-cyanate based coating

Different levels of Aloxide formation

2 alcohol plus alkyl based coating

Solar Panels Material design to on-site testing

FTIR Lab & Portable

Developing adhesives Curing studies Adhesive thickness Coating thickness Material ID Surface cleanliness Panel condition

Oils, Fuels, Lubricants Analysis by Portable FTIR

Fuel Specifications:
MTBE, ETBE, Ethanol, Total Aromatics, Total olefins, Benzene, Toluene, RON, MON, Water.

Oil/Lubricant Condition Monitoring

Identification Oil health: water, additives, nitration, soot, anti-wear, extreme pressure (based on ASTM E2412 ) Turbine Oil, Hydraulic fluid (mineral, polyol ester), Gear oil, compressor oil , Electrical insulating oil (ASTM D2668 )..

Biodiesel fuel contamination & Biodiesel blending Biodiesel is deleterious to stored diesel fuel used for back up generator for nuclear fuel rods
EN 14078 & ASTM 7371-07 specify FTIR

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FTIR Analysis of Liquids DialPath and TumblIR

1. Collect background

2. Place sample

3. Analyze the sample

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Advantages of DialPath Technology for analysis of liquids

Non-viscous and/or volatile liquids can easily fill the DialPath, even when in the close position, by simple capillary action Viscous samples (oils, syrups, etc) can easily fill DialPath in open position
3L Fill Volume

250 L Fill Volume

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Oils, Lubricants and Biodiesel in Diesel Fuel

Advantage of DialPath/TumblIR with FTIR solutions
Immediate and accurate answer
Accelerate time-to-action Reduce costs associated with fluid replacement not required (as well as cost of disposal)

Ease of use
Accelerate and simplify method transfer and training Sample throughput Limited sample handling and preparation required (no liquid cells)

In-lab and remote location monitoring

Develop methods in the lab or directly in the field Mining camps /In-vehicle testing Off-shore drilling sites

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Measuring Anti Oxidants in Oil

Phenolic DBPC, di-tertiary-butyl paracresol

O H

Aminic aDPA, alkyl di-phenylamine

N H
Absorbance
3625 3620 3615 3610

Absorbance

3680

3675

3670

3665

3660

3655

3650 3645 3640 Wavenumber

3635

3630

3460 3455 3450 3445 3440 3435 3430 3425 3420 3415 3410 340 3405 3400 3395 Wavenumber 5

Phenolic/Aminic Antioxidants in Oil

10000 9000 8000 7000 6000 5000 4000 3000 2000 1000

Quant Validation Plot for Phenolic (ppm) R=1.000

16

19

Concentration

25

10

7 13 28

22 1

0.0

0.2

0.4

0.6

0.8 Peak Area

1.0

Absorbance

1.2 3700

1.4 3690

3680

3670

3660 3650 Wavenumber

3640

3630

3620

3610

Material Identification O-ring and seals

Germanium ATR

Selectivity of FTIR is ideal for material

identification
Well suited to polymers and elastomers

Ge ATR ideal for carbon filled material Industrial need for positive ID
Chemical and manufacturing industry O-rings and seal materials Safety requirement to prevent leaks

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Material Identification O-ring and seals

Germanium ATR Identified all 10 groups of seals
Fluorosilicone, Silicone, Viton, EPR/EPDM,
Neoprene, Butyl, Kalrez, NBR, Polyurethane, Natural Rubber

Easy Identification by spectral search

Similarity = correlation
Highest correlation = correct ID

Demonstration - 15 samples
Exoscan correctly identified all samples
Only one sample had a close second Selectivity of FTIR is ideal for material identification

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Food Applications for Routine, Portable and Handheld FTIR

Identification
Incoming product ID

Verification
Food oil type (olive oil) to prevent counterfeiting

Adulteration
Used Vegetable Oils

Contamination
Ethylene glycol in glycerol

Identification of Food Additives Glycerol

5500 DialPath using 30 m path length

20 second measurement time

Results confirmed with a library search
Correct match R2 > 0.99

Glycerol
Glycerol

Propylene Glycol
Di -Propylene Glycol Triacetin

Other Related Applications

Field determination of quality traits

Total Trans Fat

App Note 5991-0003EN - In situ screening of quality traits in tomato cultivars using the handheld 4200 FlexScan FTIR Mossoba et al. (2012), J Am Oil Chem Soc, Vol. 89 (3) pp 419-429 (DOI 10.1007/s11746-011-1930-9)

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Hydrocarbon Contamination in Soil

DRIFT with PLS regression analysis Cross-validation with GC and bench-top FTIR

Ziltek, Australia (www.Ziltek.com.au)

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Algunas soluciones para la industria con la instrumentacin porttil

Mediciones en Biodiesel
Confirmar Substancias desconocidas para aplicaciones forenses. QA/QC en anlisis expedito de alimentos para confirmar ingredientes o eliminar productos en no conformidad

Anlisis ambiental de Aire, Suelo y Agua

Anlisis de Materiales, compuestos, recubrimientos y polmeros

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FTIR Porttil de Agilent

Sistemas de Espectroscopia de FTIR porttil

Sistemas de FTIR- MIR Miniaturizado Excelentes especificaciones Similares a las de un instrumento No porttil

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Exoscan 4100 y Flexscan 4200

Modos de muestreo
ATR Esfrico
ATR de diamante para identificacin de polmeros ATR de Germanio para polmeros con Carbn

Reflectancia Externa (45)

Superficies metlicas Reflectivas Oxidacin de superficies, grosor de recubrimiento y qumica

ngulo Grazing (~82)

Grosor de pelcula sobre superficies metlicas Identificacin de trazas de contaminantes

Reflectancia Difuse
Muestras no reflectivas, Compuestos de fibra de carbn

Algunos resultados de lectura

Calcitas: Lectura en dos superficies diferentes, plana y rugosa, Los espectros fueron obtenidos empleando ExoScan con Modo de reflectancia 120 Spectros Co-Add en aproximadamente 1 min, 4 cm-1 de resolucin y en el intervalo de 4500 a 650 cm-1

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Espectros de rocas y minerales empleando el ExoScan 4100

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Identificacin

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Identificacin

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Identificacin

Identificacin de Barita, el espectro de abajo fue identificado como Barita por otro mtodo, si se compara con la biblioteca del espectro de Barita, este corresponde a la calcita

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Software

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Laboratorio porttil Conclusin

Reduce Tiempo para obtener resultados Elimina el transporte de muestra Tiempo y dinero Toma de decisiones

En el lugar de muestra
Seleccin rpida muestras criticas

Incrementa productividad

Visite las pginas Web para Mediciones Moviles www.chem.agilent.com O Contact a su representante Agilent

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Porqu usar Espectroscopa de FT-IR con DialPath y TumblIR.

-Anlisis FT-IR es fcil de realizar - FT-IR proporciona resultados increblemente precisos - Los resultados estn disponibles dentro de segundos a minutos - El mtodo es muy verstil? (puede acomodar diversos tamaos y tipos de muestra) - Una potente herramienta para el anlisis de cualquier lquido . - Proporciona tanto resultados cuantitativos y cualitativos - Anlisis FT-IR es rpido y ayuda a la determinacin de compuestos voltiles,

- Espectroscopia FT-IR es un mtodo econmico.

- FT-IR se requieren muy poca o ninguna preparacin de la muestra. - Monitoreo en el sitio de muestreo.

Where to go for more information

Agilent Life Science and Chemical Analysis Homepage:
http://www.agilent.com/chem

Molecular Spectroscopy homepage (Videos, App notes, Support)

http://www.chem.agilent.com/en-US/products-services/Instruments-Systems/MolecularSpectroscopy/Pages/default.aspx

Webdemo
http://www.chem.agilent.com/en-US/promotions/Pages/ExoScan-web-demo.aspx

Speak to your local: diego.lozada@agilent.com Agilent representative / Product Specialist!

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Preguntas?

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