Diffuse Reflection

Theory and Applications

Diffuse reflection is an excellent sampling FACTORS THAT INFLUENCE
technique for powdered or crystalline SPECTRAL QUALITY
materials in the mid-IR and NIR spectral
Some powders may be analyzed by diffuse reflection as neat
ranges. It can also be used for analysis samples (coal samples, soil samples, diffuse coatings on a
of intractable solid samples. As with reflective base). Usually, the sample must be ground and
transmission analysis in the mid-infrared, often mixed with a non-absorbing matrix such as KBr. The sample
samples to be analyzed by diffuse reflection to matrix ratio is generally between 1 to 5% (by weight).
Diluting ensures a deeper penetration of the incident beam
are generally ground and mixed with an IR into the sample which increases the contribution of the
transparent salt such as potassium bromide scattered component in the spectrum and minimizes the
(KBr) prior to sampling. specular reflection component.
The specular reflection component in diffuse reflection
Diffuse reflection sampling offers an excellent spectra causes changes in band shapes, their relative
alternative to transmission of KBr pellets as it eliminates intensity, and, in some cases, it is responsible for complete
the time-consuming process of pressing pellets. This band inversions (Restrahlen bands). Dilution of the sample
technique1 can also be used to study the effects of with a non-absorbing matrix minimizes these effects.
temperature and gas flow for the analysis of catalysts Particle size and sample loading mechanics also play an
and other diffusely scattering samples by configuring the important role.
accessory with a heating or cooling environmental chamber. This is shown below in the spectral data for caffeine,
One of the greatest additional benefits of diffuse reflection where the upper spectrum is diluted to about 2% by
sampling is that it is ideally amenable to automation. Methods weight in KBr and demonstrates very high quality with
can be developed with a manual version diffuse reflection sharp, well-defined absorbance bands. The lower spectrum
accessory and then moved to automation to increase sample is of undiluted caffeine measured by diffuse reflection
throughput. PIKE Technologies offers several diffuse reflection and shows derivative-shaped bands in the 1700 cm-1 and
accessory configurations: basic, advanced with heat chamber 1500 cm-1 region of the data. The upper spectrum of diluted
capabilities, upward directed IR beam for easy sampling caffeine is clearly of higher spectral quality than that of the
access and fully automated for maximum sampling efficiency. undiluted caffeine.

HOW DIFFUSE
REFLECTION WORKS
Diffuse reflection relies upon the focused projection of the
spectrometer beam into the sample where it is reflected,
scattered and transmitted through the sample material. The
back reflected, diffusely scattered light (some of which is
absorbed by the sample) is then collected by the accessory
and directed to the detector optics. Only the part of the beam
that is scattered within a sample and returned to the surface
is considered diffuse reflection.

Diffuse reflection spectra showing greatly improved results from

Incident Radiation sample dilution.

Specular Reflection
Other factors related to high spectral quality for diffuse
Diffuse Reflection reflection sampling are listed below.
▶ Particle Size – reducing the size of the sample particles
reduces the contribution of reflection from the surface.
Smaller particles improve the quality of spectra
(narrow bandwidths and better relative intensity). The
recommended size of the sample/matrix particles is
50 microns or less (comparable to the consistency
 Diffuse Reflection
of the finely ground flour). This fine powder is The Kubelka-Munk equation creates a linear relationship
easily achieved by using the PIKE Technologies for spectral intensity relative to sample concentration (it
ShakIR ball mill. assumes infinite sample dilution in a non-absorbing matrix,
▶ Refractive Index – effects result in specular reflection a constant scattering coefficient and an “infinitely thick”
contributions (spectra of highly reflecting samples sample layer). These conditions can be achieved for highly
will be more distorted by the specular reflection diluted, small particle samples (the scattering coefficient
component). This effect can be significantly reduced by is a function of sample size and packing) and a sample
sample dilution. layer of at least 1.5 mm. With proper sample preparation,
▶ Homogeneity – samples prepared for diffuse diffuse reflection spectroscopy can provide ppm sensitivity
reflection measurements should be uniformly and and high-quality results.
well mixed. Non-homogenous samples will lack
PLASTIC BUMPERS AND TOUGH SAMPLES
reproducibility and will be difficult to quantify. An ideal
way to mix samples for diffuse reflection is by using the Sometimes it is necessary to analyze a sample which simply
PIKE Technologies ShakIR. does not fit in a spectrometer’s sample compartment – the
analysis of polymer-based automotive components or painted
▶ Packing – the required sample depth is governed
panels are typical examples.
by the amount of sample scattering. The minimum
necessary depth is about 1.5 mm. The sample should A special diffuse reflection technique allows quick and simple
be loosely but evenly packed in the cup to maximize IR analysis of such samples in a relatively non-destructive
beam penetration and minimize spectral distortions. manner. A small amount of the sample can be collected
by abrasion on a diamond or silicon carbide abrasion
THE KUBELKA-MUNK EQUATION disk and analyzed immediately with the help of a diffuse
reflection accessory.
Even with all these sample preparation practices, the raw The figure below shows the diffuse reflection spectrum of an
diffuse reflection spectra will appear different from its automotive body component. The PIKE Abrasion Sampling
transmission equivalent (stronger than expected absorption Kit with diamond sampling disk was rubbed across the
from weak IR bands). A Kubelka-Munk conversion can be large automotive component which collects some of the
applied to a diffuse reflection spectrum to compensate for polymer material into the web of the sampling disk. Spectra
these differences. This conversion is available in most FTIR were co-added for 1 minute and ratioed to the diamond disk
software packages. background spectrum. The resulting spectrum is of excellent
The Kubelka-Munk equation is expressed as quality and is identified as a polypropylene copolymer.
Diffuse reflection can also be used for the analysis of liquid
samples. In this application a small amount of the sample is
dispensed directly onto the KBr powder and analyzed.

where R is the absolute reflectance of the sampled

layer, k is the molar absorption coefficient and s is the
scattering coefficient.

Diffuse reflection spectrum using diamond abrasion disk.

POWDERS
For the analysis of powders the following procedure
Diffuse reflection spectra of ibuprofen with Kubelka-Monk conversion is recommended:
compared to a transmission spectrum.
▶ Place about 200–400 mg of KBr into the ShakIR
The spectra shown above demonstrate this spectral ball mill vial with a stainless steel ball and
conversion for ibuprofen collected by diffuse reflection. The grind for 30 seconds
sample was diluted to about 1% by weight in KBr and mixed ▶ Fill the background diffuse cup with this KBr
using the ShakIR. The Kubelka-Munk converted spectrum for ▶ Remove excess KBr with a flat edge – the KBr should
ibuprofen shows excellent comparison with the transmission be loosely packed
spectrum and is easily identified using library search of a ▶ Add 1 to 5 mg of the sample to the remaining KBr in the
transmission spectral database. ShakIR vial and mix for 30 seconds
▶ Fill the sample diffuse cup with this mixed sample/KBr
 ▶ Remove excess sample with a flat edge – the sample
should be loosely packed
▶ Place the background and sample diffuse cups into
the sample holder
▶ Slide the sample holder into the accessory
▶ Position the KBr cup in the beam and
collect a background
▶ Move the holder to the sample position and collect a
sample spectrum (the ratio of these two spectra will
produce a spectrum of the sample)
▶ Convert the raw diffuse reflection spectrum
to Kubelka-Munk

Under ideal conditions the transmission of the strongest

band in the spectrum should be in the 50% range. If the
resulting bands are too intense or distorted, further dilute the
sample and make sure that all other measurement affecting
factors (particle size, homogeneity and packing) are within
required limits.
SUMMARY
Diffuse reflection accessories make the analysis of a wide
range of solid samples easier, faster and more efficient.
Advanced options for diffuse reflection provide the ability to
heat and cool the sample and monitor a reaction process.
Automation versions of diffuse reflectance accessories
provide the ability to greatly increase sample throughput.

© 2021 PIKE Technologies, Inc. 6125 Cottonwood Drive, Madison WI 53719 | 608.274.2721 | [email protected] | www.piketech.com
Diffuse Reflection
Notes