What is needed to construct a NIR instrument?

NIR SPECTROSCOPY
Instruments

A light source A dispersive unit (monochromator) A detector (Fibres) (Absorbance/reflectance-standard)

Ume 2006-04-10 Bo Karlberg

The light source

The tungsten (W) lamp is the most common light source Relatively long life-time A lamp change should not change instrument performance

The light source

Light emitting diodes (LEDs) have been proposed as NIR light sources = an ideal concept! Not ready for real applications yet

Some dispersive principles

Filter: two types (minimum) a) Fabry-Perot interference filter b) AOTF (acousto-optical tunable filters) Holografic grating The interferometer principle (FT-NIR)
Sample

Discrete filter systems

Source

Interference Filters Single and double beam configurations UV/visible, Near-Infrared, mid-Infrared filters 1 - 44 Filters

Reflectance Detectors

Non-contact for solids Filter Wheel Sample cells, single fibers, fiber bundles for liquids Fast, rugged, inexpensive

Transmission Detector

Acoustic Optical Tunable Filter (AOTF)

Acoustic wave
Wavelength selected by radio frequency
Detector

AOTF
Tellurium oxide, birefringent crystal Acoustic waves change the refractive index of the material Polychromatic light radiated onto one side of the crystal comes out as two monochromatic beams on the other side

TeO2 crystal

Sample

Near-Infrared (1000 2000 nm) Tellurium oxide crystal

Radio Frequency Oscillator

Sampling with single fibers and micro-bundles

AOTF
Advantages: no moving parts adjustable intensity narrow beams Disadvantages: difficulties when measuring highly absorbing samples limited wavelength range

Monochromator NIR

Digitally synchronous holographic grating system

Wavelength Standards
Reflectance Detectors

We distinguish between pre-dispersive and post-dispersive configurations

PRE-DISPERSIVE

Reference

Sample
Transmission Detectors

Light source

Monochromator

Sample

Detector

Sample Scan

Reference Scan

Wavelength Std..

Sample Spectrum

We distinguish between pre-dispersive and post-dispersive configurations

POST-DISPERSIVE

FT-NIR
FT = Fourier Transform

Light source

Sample

Monochromator

Detector

How does it work?

First, we have to distuingish between: Frequency domain spectroscopy and Time domain spectroscopy

Frequency domain spectroscopy

A
in nm or cm-1

Interferogram

Time domain spectroscopy

P(t)
P(t) is the time domain power

time

Interferogram

No detector can register waves at the speed of light however:

time domain spectra can be created through application of interferometric approaches

The interferometer principle

Fourier transform = the time domain spectrum is transformed to a frequency domain spectrum

Outline:

CE

MEKC

FTIR-CE

Results

QCL

Results

Conclusion

The Michelson interferometer

The Michelson interferometer

Source Beam Splitter Sample

Non-dispersive system with white light illumination Mechanical or magnetic drive mechanism
Fixed Mirror

Detector

Single beam rapid scanning of reference and sample Co-addition of spectra to improve signal-to-noise

Moving Mirror

Sampling attachment

SAMPLE

Outline:

CE

MEKC

FTIR-CE

Results

QCL

Results

Conclusion

The wishbone interferometer

Collimated Beam from Source

The wishbone design

a b c d e

Wishbone Anchor Flex pivot (2) Cube corner mirrors Beam Splitter

e Collimated Beam to Sample e b c d

Double pendulum

The crystal interferometer

Linear Motor for Scanning Beam Splitter Lens Source LED Lens S a m p l e Detector

Dispersion principles, summary

NIR: filter, grating and FT instruments are equally common on the market (roughly) mid-IR: total domination of FT instruments

Polarization Filter

Polarization Filter Quartz Lens Crystals

Beam Splitter

Lens

Reference Detector

Detectors, NIR
Silicon detector, up to 1100 nm, stable, rapid, reliable, inexpensive Lead sulphide, 900-2600 nm, a common NIR detector, established, a little slow response InGaAs (indium gallium arsenide), 800-1700 nm, 1300-2200 nm, 1500-2500 nm, expensive
A r r a y

The diode-array design

Sample
Source

UV/visible, Near-Infrared Silicon Array (Si) 400-1100 nm Lead Sulfide (PbS) 1100-2500 nm Indium Gallium Arsenide (InGaAs) 800-1600 nm Sample cells, fiber optic bundles Resolution is determined by the number of elements in the array

Fixed Grating

Scanning NIR systems

System Holographic Gratings Advantages Rapid Scanning High Dynamic Range Rugged (Digital) Extend Scan Ranges Rapid Scanning Large Aperture Fast Scanning Fast Stepping Disadvantages Moving Parts

Qualitative analysis
Identification of various substances (often very pure) Classification

Interferometers

Moving Parts Environmentally Sensitive (Varies) Bandpass Variation Moving Parts Spectral Artifacts Bandpass Variation RF & Temperature Sensitive Unique Components (Crystal) Limited Wavelength (Cost) Limited Dynamic Range Temperature Sensitive Pixel Variations

AOTF

Diode Arrays

No Moving Parts Rapid Scanning Rugged

Qualitative analysis
In this case the spectral resolution is of large importance

Quantitative analysis

In this case the signal-to-noise ratio is of large importance A S/N

Probe types

Sample presentation, NIR

Transmission Pair
Source Detector
Sample

Interactance Immersion

Mirror

Sample

Reflectance Probe

Sample

Contact Probes: Transmission

Contact probes: Immersion

Illumination Fibers

Sapphire Lens Spacer

Collection Fibers

Path length = 2 x Gap Gap = 1.0 to 20 mm

Sapphire windows

Fiber bundles

Spacers for fixed path lengths (1 to 40 mm) 316 Stainless steel or other metals Ratings: 300C at 5000 psi (350 atm) Metal to sapphire seals

0 to 15% Total solids 316 Stainless steel or other metals Ratings: 300C at 5000 psi (350 atm) Metal to sapphire seals

Contact probes: Reflectance

4

Fiber optics vs. length

3.5 3 Absorbance 2.5 2 1.5 1 0.5 0 1100 1300 1500 1700 1900 2100 2300 14m 16m 25m 38m 46m 78m

Diffuse reflectance
Sapphire window

Fiber bundles 316 Stainless steel or other metals Ratings: 300C at 5000 psi (350 atm) Metal to sapphire seals

Wavelength

Multiplexer systems
Sample points

Side-stream sampling
Analog/Digital outputs to PLC or DCS

Process analyzer
Multiplexer module

Transmission, Interactance & Reflectance Probes 316 Stainless Steel Construction 1 in. Swagelok Fittings for Probes 0.5 & 1.0 in. NPT for Sample Stream

Process PC

Fiber optics

Multiple sample points per instrument Sequential analysis Reduced cost per measurement point