1993 Mitchell Drift

13
Fundamentals and Applications

of Diffuse Reflectance Infrared Fourier
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Transform (DRIFT) Spectroscopy

Publication Date: May 5, 1993 | doi: 10.1021/ba-1993-0236.ch013
Mark B. Mitchell
Department of Chemistry, Clark Atlanta University, Atlanta, G A 30314
Diffuse reflectance spectroscopy is a powerful tool for the study of

materials such as polymers and catalysts. The bulk or surface mor-
phology of these materials is many times an important experimental
parameter that can be altered by sample preparation methods used in
the more common spectroscopic techniques. Diffuse reflectance in-
frared Fourier transform (DRIFT) spectroscopy has been shown to be
more sensitive to surface species than transmission measurements and
to be an excellent in situ technique. The applications of DRIFT
spectroscopy to the investigation of polymer surfaces and surface
structures of both fibers and films are particularly germane to this
symposium and are covered in this review. The foundations of the
diffuse reflectance technique in the mid-infrared range are presented,
and methods that have been used to obtain spectra for polymer
powders, films, and fibers are outlined, as is the use of DRIFT
spectroscopy for depth-profiling studies. The use of DRIFT spec-
troscopy for the investigation of catalytic processes is also reviewed.
DIFFUSE REFLECTANCE INFRARED FOURIER TRANSFORM (DRIFT) spec

troscopy is an infrared sampling m e t h o d that involves m i n i m a l sample p r e p a
ration i n terms o f time a n d sample manipulation. D R I F T spectroscopy is
particularly useful f o r p o w d e r samples, b u t c a n also b e used to investigate
samples such as p o l y m e r fibers a n d films. T h e manipulations i n v o l v e d i n
preparation o f a sample f o r transmission measurements, as a n example,
involve m i x i n g the sample w i t h an appropriate diluent a n d compressing the
0065-2393/93/0236-0351$07.25/0
© 1993 American Chemical Society
In Structure-Property Relations in Polymers; Urban, M., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1993.
352 STRUCTURE-PROPERTY R E L A T I O N S IN POLYMERS
sample into a transparent pellet. T h i s preparation can easily result i n irre

versible changes i n sample m o r p h o l o g y a n d surface properties. T h u s , m i n i
m i z i n g sample manipulation becomes an important consideration w h e n
sample m o r p h o l o g y a n d surface properties are investigated, or are important
sample variables. I n addition, because the sample is not compressed for
D R I F T spectroscopy, good gas contact w i t h the entire sample is possible, a
distance advantage for i n situ measurements. Gas flow t h r o u g h the sample is
a capability that makes D R I F T spectroscopy useful as one segment o f a
hyphenated analytical system or as a technique for the study o f gas-surface
interactions.
D i f f u s e reflectance has b e e n used extensively i n the visible a n d ultravio
let regions o f the electromagnetic spectrum for the characterization o f solid
materials such as inorganic powders. M a n y o f the effects a n d constraints that
govern diffuse reflectance spectroscopy were d e t e r m i n e d as a result o f

experiments w i t h ultraviolet a n d visible radiation. I n those investigations, the
K u b e l k a - M u n k expression was particularly useful for relating the observed
reflectance spectrum to the optical constants o f the material u n d e r study.
References b y W e n d l a n d t a n d H e c h t ( I ) a n d b y K o r t u m ( 2 ) provide an
excellent b a c k g r o u n d a n d i n c l u d e reviews o f these earlier investigations.
I n 1976, W i l l e y ( 3 ) d e s c r i b e d the optical design o f an instrument
developed to extend the technique o f diffuse reflectance into the infrared.
H i s F o u r i e r transform I R ( F T I R ) spectrometer was specifically designed to
carry out i n f r a r e d diffuse reflectance measurements, although it c o u l d also be
used for transmission measurements.
Since the w o r k o f F u l l e r a n d Griffiths i n 1978 a n d 1980 (4, 5), the
D R I F T spectroscopy technique has b e e n u s e d for the analysis o f a w i d e
variety o f sample types, i n c l u d i n g p o l y m e r powders, films, a n d fibers; hetero
geneous catalysts; a n d high-temperature superconductors, as w e l l as " n o r m a l "
inorganic a n d organic p o w d e r materials. F u l l e r a n d Griffiths l a i d m u c h o f the
groundwork necessary for the use o f the technique as an analytical tool. T h i s
review outlines the foundation l a i d b y F u l l e r a n d G r i f f i t h s and by other
investigators a n d presents results that demonstrate the utility of the D R I F T
spectroscopy technique for a variety of sample types.
A variety o f i n f r a r e d spectroscopic methods are available for use to
investigate polymers, and many o f the applications o f these techniques to
polymers have b e e n discussed (6). Transmission spectroscopy is one o f the
most c o m m o n methods, but, as m e n t i o n e d earlier, the pressure n e e d e d to
f o r m pellets o f many polymers can affect surface functionality. These effects
were d o c u m e n t e d b y B l i t z et al. ( 7 ) i n their investigation o f trimethoxymeth-
ylsilane o n a silica surface. T h e authors showed that the pressures i n v o l v e d i n
m a k i n g a pellet i n d u c e d c h e m i c a l changes i n the surface functional groups.
A l s o , many samples o f interest simply are not optically t h i n enough to be
studied b y transmission. F i b e r - r e i n f o r c e d composites are an example o f such
a case.

13. MITCHELL Diffuse Reflectance IR Fourier Transform Spectroscopy 353
Attenuated total reflectance ( A T R ) is one o f the best ways to obtain

i n f r a r e d spectra o f p o l y m e r films. O n e o f the requirements o f A T R is that the
sample make optical contact w i t h a n i n f r a r e d crystal. Some samples are n o t
soft enough to f o r m g o o d contact a n d are difficult to study w i t h this m e t h o d .
F i b e r s are very difficult to measure w e l l using A T R .
C h i l d e r s a n d P a l m e r (8) a n d U r b a n et a l . ( 9 ) c o m p a r e d photoacoustic
spectroscopy ( P A S ) a n d D R I F T spectroscopy. T h e general conclusion is that
the methods are comparable: D R I F T spectroscopy usually gives better signal
to noise ( S / N ) ratios f o r most samples, b u t P A S is better suited for strongly
absorbing or highly reflective samples. A n o t h e r general conclusion is that

D R I F T spectroscopy is very sensitive to sample morphology (with p o w d e r
particle size b e i n g a critical parameter), whereas P A S is relatively insensitive
to sample morphology a n d is perhaps better suited to the study o f carbon-filled
rubbers, for example, because it is difficult to control particle size f o r a

D R I F T sample. P A S c a n b e used f o r depth-profiling ( 9 , 10), w h i c h is not as
easily accomplished using D R I F T spectroscopy, although some concentration
versus d e p t h i n f o r m a t i o n c a n b e generated using D R I F T w i t h K B r overlayers
as is discussed later.
Theory
T h e r e are t w o general types o f reflected light: specular a n d diffuse. A
c o m m o n example o f specular reflection (also called front-surface, regular, o r
F r e s n e l reflection) is light reflected f r o m mirrors o r other p o l i s h e d surfaces.
Specular reflectance occurs at any interface between t w o materials w i t h
different refractive indices. Specularly reflected light is characterized b y the
rule that the angle o f reflection is equal to the angle o f incidence. C o m m o n
examples o f diffusely reflecting surfaces are the matte surfaces characteristic
o f certain types o f paper a n d powders. D i f f u s e l y reflected radiation is the
fight reflected f r o m a diffusely reflecting sample f o r w h i c h the angle o f
reflection does not equal the angle o f incidence.
Optical Constants. T h e intensive property that characterizes t h e

reflectance a n d transmittance o f a material is the complex refractive index
(n ), w h i c h is the s u m o f t h e index o f refraction (n) (called t h e real
f
component) a n d the absorption index (k ) (called the imaginary component):

f
ri = η + ik' (1)
F o r nonabsorbing materials, k' = 0. Specularly reflected light is w e l l d e

scribed b y FresneFs equations (see reference 1), w h i c h express the reflection
o f electromagnetic radiation at an interface as a function o f the refractive
indices o f the t w o m e d i a that f o r m t h e interface. T h e difference i n the
refractive indices leads to reflection. T h e differences i n refractive index that

354 STRUCTURE -PROPERTY RELATIONS IN POLYMERS
l e a d to reflection can be due to differences i n the real o r the imaginary

components.
I n the B e e r - L a m b e r t equation, the loss o f transmitted intensity, I, due
to absorption processes is given b y
I = I e- *
0
k
(2)
w h e r e k is the absorption coefficient (Φ k') a n d χ is the path length t h r o u g h

the sample. T h e absorption index is related to the absorption coefficient b y
Jfc'=Jfc/4irv (3)
w h e r e ν is the frequency o f the radiation (per centimeter) a n d the absorption

coefficient is related to the absorptivity, a, a n d the concentration, c, o f a n

absorber b y
k = 2.303ac (4)
Kubelka-Munk Expression. I n any spectroscopic technique it is

important to be able to characterize the response o f the technique to the
concentration o f the analyte. A n u m b e r o f models have b e e n d e v e l o p e d that
y i e l d expressions relating observed diffuse reflectance to concentration ( J , 2,
9). T h e n u m b e r o f i n d e p e n d e n t experimental variables that must b e evalu
ated for each expression is related to the complexity o f the m o d e l . T h e most
c o m m o n l y u s e d expression is the two-parameter K u b e l k a - M u n k ( K M ) ex
pression ( I , 2, 11-13):
f(R )
œ = (l-R f/2R^-k/s
œ (5)
w h e r e R is the absolute reflectance o f an " i n f i n i t e l y t h i c k " sample,

x f(R )
œ
represents the value o f the K u b e l k a - M u n k f u n c t i o n , k is the absorption

coefficient d e f i n e d previously, a n d s is a scattering coefficient d e f i n e d for
p u r e l y scattering samples b y
1 = I e~"
0 (6)
It is generally assumed that s is a constant or at most a slowly varying

function o f frequency a n d is not a f u n c t i o n o f analyte concentration. A n
infinitely thick sample is one t h r o u g h w h i c h no light is transmitted. A l l light is
either reflected or absorbed. T h e infinitely thick criterion is generally satis
fied for samples that are 3 - 5 m m thick. T h i s thickness does not satisfy the
infinitely thick c r i t e r i o n for a l l samples or for many samples over the w h o l e
m i d - i n f r a r e d range; these considerations are discussed later. Nonetheless,
D R I F T spectra o f most c o m p o u n d s can be at least semiquantitative w i t h
samples o f this thickness. A s an aside, Fraser a n d G r i f f i t h s (14) argue that

because the effective path length increases b y a factor o f 2 f o r diffuse

reflectance, eqs 2 a n d 6 s h o u l d b e m o d i f i e d such that the exponents are
— 2 fee a n d — 2sx, respectively. I n p r i n c i p l e , this change s h o u l d have no
effect o n the remission f u n c t i o n ( e q 5) calculated f o r the infinitely thick
sample, because the factor o f 2 w i l l cancel. H o w e v e r , this possible discrep
ancy s h o u l d b e kept i n m i n d w h e n c o m p a r i n g k data f r o m different groups.
Typically, the absolute reflectance o f e q 5 is not evaluated. Instead, the
reflectance relative to some nonabsorbing standard is measured. R is f
œ
substituted f o r R i n e q 5, w h e r e
œ
R' = R (sample)/Β»
œ œ (standard) (7)
R (sample) is the reflectance o f the sample a n d R (standard) is the

œ œ
reflectance o f a nonabsorbing standard, such as K B r o r K C l . F o r samples that

obey the K u b e l k a - M u n k expression, plots o f f(R'«) versus concentration (c)
y i e l d a straight line w i t h a slope o f 2 . 3 0 3 « / s .
I n their original paper, F u l l e r a n d Griffiths (4) presented results that
showed the dependence o f the D R I F T spectra o n particle size a n d concen
tration o f the absorber. Plots o f the K M intensity o f a particular b a n d showed
deviations f r o m linearity at h i g h absorber concentrations. T h e K M equation is
d e r i v e d w i t h the assumption that the sample is optically dilute: the concentra
tion o f the absorber is l o w o r the absorption coefficient is small. T h i s
condition is generally m e t b y d i l u t i n g the sample o f interest i n a nonabsorb
ing matrix such as K B r o r K C l , although for weak i n f r a r e d absorptions, this is
not necessary. F o r samples that satisfy the optically dilute criterion, small
changes i n concentration result i n p r o p o r t i o n a l changes i n the observed K M
intensities.
Fresnel Reflection. T o a i d a discussion o f several o f the causes a n d

possible solutions o f nonlinearity associated w i t h D R I F T spectroscopy, it is
useful to consider the sample material as a composition o f small grains o f
diluent a n d analyte (see F i g u r e 1). W h e n radiation interacts w i t h the sample,
three different events, w h i c h y i e l d three classes o f reflected radiation, c a n
occur. T h e first class results f r o m the simple reflection o f incident radiation at
a sample grain interface that is parallel to the macroscopic surface o f the
sample; this is c a l l e d specular F r e s n e l reflectance, after B r i m m e r a n d G r i f
fiths (15). T h i s reflection f r o m the t o p surface o f the p o w d e r is n o t isotropi-
cally scattered; the angle o f reflection is e q u a l to the angle o f incidence. T h e
reflection f r o m the t o p surface also retains the polarization o f the incident
beam.
T h e second class o f reflected radiation is similar to the first i n that it is
not transmitted t h r o u g h any sample grains. M a n y o f the grain interfaces that
the radiation encounters w i l l not b e parallel to the surface o f the macroscopic
sample. Incident radiation that encounters such an interface w i l l b e reflected

356 STRUCTURE-PROPERTY RELATIONS IN POLYMERS
Incident Radiation
Figure 1. Schematic diagram of the DRIFT interaction with three classes of

interaction shown. The top ray is used to indicate the Fresnel specular component
of the reflected radiation, which is reflected from the first interface it encounters
at the top of the sample. The center ray indicates the Fresnel diffuse component.
After two reflective interactions and no transmission through any sample grain,
the sample is reflected out of the sample. The lowest ray corresponds to the
Kubelka-Munk diffuse reflectance, which is radiation that has been reflected
from some grains and transmitted through others.
at an angle that is equal to the angle o f incidence at t h e grain interface, yet

not equal to the angle o f incidence to the macroscopic sample. T h i s radiation
w i l l carry n o i n f o r m a t i o n about the analyte, b u t it is diffusely reflected i n the
sense that it is isotropically scattered a n d its polarization is scrambled relative
to that o f the incident radiation. T h i s radiation is called diffuse Fresnel
reflectance. M u l t i p l e reflection w i t h i n the sample w i l l also generate radiation
e m e r g i n g f r o m the sample that has not b e e n transmitted through any sample
grain, a n d this radiation falls into the class o f diffuse F r e s n e l reflectance.
T h e t h i r d a n d final class o f radiation reflected f r o m the sample is called
the diffuse K u b e l k a - M u n k reflectance. T h i s radiation has b e e n transmitted
t h r o u g h at least one sample grain, contains a l l the i n f o r m a t i o n regarding the
analyte that is available i n the reflected radiation, is isotropically scattered,
and its polarization is s c r a m b l e d relative to the incident field. T h e intensity o f
this radiation obeys the K u b e l k a - M u n k relation f o r the intensity o f analyte
absorption bands relative to concentration o f the absorber, u n d e r the l i m i t a
tions o f that relation.
The presence o f F r e s n e l reflectance i n the radiation collected b y
the detector leads to m u c h o f the nonlinearity associated w i t h DRIFT

spectroscopy. Specular F r e s n e l reflectance is relatively easy to eliminate f r o m

the collected radiation. O n e scheme is to collect radiation i n directions that
exclude the plane o f incidence o f the incident radiation (16, 17). A second
scheme is to polarize the incident radiation a n d collect radiation t h r o u g h an
analyzing polarizer oriented at 90° to the polarization o f the incident radiation
(17, 18). These two optical configurations are illustrated i n F i g u r e 2. N e i t h e r
o f the two methods w i l l eliminate the diffuse F r e s n e l reflectance. O n e
m e t h o d that apparently decreases diffuse F r e s n e l reflectance is to g r i n d the
sample a n d diluent to very small particle sizes. T h i s m e t h o d decreases the
fraction o f incident radiation that is reflected out o f the sample without b e i n g

transmitted t h r o u g h a sample grain.
F r e s n e l reflectance does not obey the K u b e l k a - M u n k relation w h e t h e r
specularly or diffusely reflected, a n d it is important to k n o w w h e n an
observed spectrum can be characterized using the K u b e l k a - M u n k relation.

Intensity variations i n the F r e s n e l reflectance components o f the collected
radiation are directly dependent o n variations i n b o t h the index o f refraction
(n) a n d the absorption index (k ) o f the sample. I n the n e i g h b o r h o o d o f an
f
absorption b a n d , the index o f refraction fluctuates rapidly as a f u n c t i o n o f

frequency a n d takes o n the first derivative shape characteristic o f a d a m p e d
oscillator. T h i s fluctuation is k n o w n as anomalous dispersion. F o r moderate to
weak absorption bands, the F r e s n e l reflectance is d o m i n a t e d b y the fluctua
tions o f the index o f refraction, a n d spectra that contain a large F r e s n e l
reflectance c o m p o n e n t w i l l show characteristic derivative-shaped bands. F o r
absorption bands w i t h very h i g h absorption indices, the F r e s n e l reflectance is
d o m i n a t e d b y the absorption index, a n d the sample is actually m o r e reflective
i n the n e i g h b o r h o o d o f these absorption bands than i n spectral regions i n
w h i c h the sample is transparent. These " i n v e r t e d " reflectance bands are
called reststrahlen bands. A n o m a l o u s dispersion a n d reststrahlen bands a n d
their effects have b e e n discussed b y several groups (16, 18-20).
W i t h respect to the absorption index scale, strong i n f r a r e d chromophores
such as the 6 7 4 - c m C - H out-of-plane absorption o f benzene have absorp
- 1
tion indices o n the order o f 1.5 (21). T h e weakly absorbing C - H stretch

vibrations o f benzene have absorption indices o f 0 . 0 1 - 0 . 0 5 . F o r inorganic
materials, the absorption indices associated w i t h m e t a l - o x y g e n a n d
m e t a l - h a l i d e vibrations can be significantly greater than 3.0. S u c h absorp
tions almost always lead to distorted peak shapes w h e n measured u s i n g
D R I F T spectroscopy.
Optical Accessories. Several companies manufacture optical acces

sories that can be u s e d to obtain D R I F T spectra. T h e majority o f these
accessories correspond to one o f the configurations shown i n F i g u r e 2 A a n d
B . H o w e v e r , the on-line configuration is used most c o m m o n l y without the
polarizers. U n d e r such conditions, the o n - a n d off-line configurations p e r f o r m
m u c h differently w i t h regard to their ability to reject F r e s n e l reflectance.

Analyzer
Radiation from
To detector
interferometer
Polarizer
[] Sample
(A)
Radiation from To detector

interferometer
U Sample
(B)
Radiation from
interferometer
Detector
Analyzer
(C)
Figure 2. Schematic diagram of three commonly used optical configurations that
eliminate to a great degree the contribution of Fresnel specular reflectance to
the collected radiation. The top diagram (A) represents the in-line configuration
in which polarizers are used to eliminate the specular component. The middle
diagram (B) shows the off-line configuration in which exclusion of the plane of
incidence from the collection optics is used to eliminate the specularly reflected
component. The bottom diagram (C) is a configuration built by Fuller and
Griffiths (3). (Reproduced with permission from reference 17. Copyright 1948.)

Comparisons o f these two configurations have b e e n carried out b y at least

three groups (16-19), a n d it was observed that the optical off-hne configura
tion leads to better rejection o f the F r e s n e l components o f the reflected
radiation than the on-line configuration w h e n the polarizers are not used f o r
the optical i n - l i n e configuration. H e m b r e e a n d S m y r l ( 1 9 ) observed that even
for relatively weak c a l c i u m carbonate absorptions, the on-fine configuration
gave nonlinear results as a f u n c t i o n o f concentration even at l o w concentra
tions. T h e use o f a device to physically b l o c k specularly reflected radiation
i n the on-line configuration significantly r e d u c e d the throughput o f the
configuration.
Sample Preparation. O n e o f the limitations o f diffuse reflectance

spectroscopy w i t h regard to its use as a truly quantitative technique involves
the reproducibility o f the technique. Because the sample materials are

typically powders, the physical characteristics o f the diluent a n d the analyte
play a n important role i n the reproducibility o f the results.
I n their first paper, F u l l e r a n d Griffiths (4) investigated the effects o f
particle size o n the observed spectra. T h e spectra were clearly shown to b e
dependent o n particle size, a n d samples w i t h smaller average particle sizes
(average particle size < 10 μ ι η ) gave better spectra w i t h r e d u c e d peak
widths c o m p a r e d to samples w i t h large average particle sizes (average particle
size > 90 μ ι η ) . A n average particle size o f 10 μ m is a realistic goal f o r
quantitative measurements o f powders. Average particle sizes o f 5 0 - 1 0 0 μ m
have b e e n shown to y i e l d useful qualitative results (22). F u l l e r a n d Griffiths
also illustrated the requirement for optically dilute samples; they c o u l d not
effectively carry out spectral subtraction over large frequency ranges unless
the sample was d i l u t e d i n a nonabsorbing matrix such as K C l . L a t e r studies
b y G r i f f i t h s ' group a n d b y other groups showed that it is not always a
requirement that the sample b e diluted; p o l y m e r films a n d fibers are a n
important example o f systems that c a n b e examined without dilution, i n many
cases w i t h excellent results (see later discussion).
W i t h regard to the use o f pressure as a way to overcome the n o n r e p r o -
ducibility i n the observed spectra associated directly w i t h the sample prepara
tion step, Y e b o a h et a l . (23) f o u n d that the K M intensities o f t w o o f the
i n f r a r e d absorption bands o f caffeine increased b y almost an order o f
magnitude between a sample p r e p a r e d w i t h n o pressure treatment a n d one
subjected to a pressure o f 1 2 , 0 0 0 p s i for 5 m i n . T h i s increase i n / ( l O was
p r e s u m e d to b e completely due to a corresponding decrease i n the scattering
coefficient, an effect that (as they point out) is c o m m o n l y observed i n
pressing pellets for i n f r a r e d analysis. T h i s decrease occurs because the
scattering at a K C l - a n a l y t e interface is less than the scattering at a c o m b i n a
tion K C l - a i r - a n a l y t e interface because the refractive index f o r K C l is similar
to that f o r many organic analytes. F o r diffuse reflectance measurements
though, once the sample becomes transparent, the K u b e l k a - M u n k f o r m u l a
tion is n o longer valid because diffuse reflectance is n o longer the dominant

process. I n general, pressure increases the spectral contrast o f the observed

spectra a n d increases the r e p r o d u c i b i l i t y between measurements; the stan
d a r d deviation approaches ± 3 % for samples p r e p a r e d w i t h the same pres
sure a p p l i e d for the same length o f t i m e . H e m b r e e a n d S m y r l ( 1 9 ) also
investigated the use o f pressure as a way o f i m p r o v i n g reproducibility a n d
f o u n d that b y careful sample preparation without pressure, the standard
deviation approached + 3 % . T h e use o f pressure was f o u n d to decrease the
magnitude o f the diffusely reflected radiation and increase the specular
component.
T h e effect o f using infrared-absorbing materials as diluents was investi

gated b y B r i m m e r a n d Griffiths (24). A n important example o f such a
situation is a surface layer o n a p o l y m e r fiber or film. A l t h o u g h the p o l y m e r
fiber or film substrate is not technically a diluent i n such a sample, many o f
the considerations that B r i m m e r a n d Griffiths discuss are applicable. I n situ

catalytic studies also provide an example o f a case w h e n the use o f diluents is
not desirable. A s a diluent, K C l is a source o f many potential uncertainties i n
such an investigation: Potassium is a w e l l k n o w n p r o m o t e r i n many catalytic
systems a n d c h l o r i d e ions can act as a catalyst poison, so the use o f these
materials for i n situ investigations can clearly distort results. I n such cases, it
is many times preferable to dilute the sample w i t h a chemically inert support
material such as a l u m i n a o r silica, b o t h o f w h i c h , however, have strong
absorptions i n the infrared. B r i m m e r a n d Griffiths r e p o r t e d that the effect o f
an absorbing matrix is very complex. I n general, the authors observed an
apparent decrease i n the absorptivity o f analyte bands that o c c u r r e d i n
regions o f i n f r a r e d absorption b y the diluent. T h e authors postulated two
possible causes. T h e increased average absorption o f the sample c a n result i n
a decrease i n the effective penetration d e p t h o f the radiation into the
powder. A l s o , because the absorption index (&') for the diluent is nonzero i n
frequency regions w h e r e it absorbs, m o r e specular reflectance f r o m the front
surface o f the sample p o w d e r may be observed i n those regions than i n the
case o f a nonabsorbing diluent. T h e c o m b i n e d result is that the use o f
infrared-absorbing diluents may significantly distort analyte absorption bands,
especially the intensity o f one analyte b a n d relative to another, c o m p a r e d to
absorption bands observed i n a transmission spectrum.
Recently, Frasier a n d Griffiths (14) investigated the effect o f changes i n
the scattering coefficient s (eq 6) o n the observed D R I F T spectra; specifi
cally, the effect o f the scattering coefficient o n the infinite-depth criterion o f
the K u b e l k a - M u n k expression. T h e scattering coefficient o f K C l p o w d e r that
h a d b e e n pressed slightly, for samples o f thicknesses greater than about 500
μπι, was f o u n d equal to 25 c m , a n d the scattering coefficient v a r i e d as a
- 1
f u n c t i o n o f frequency (although b y n o m o r e than about a factor o f 2 over the

m i d - i n f r a r e d range) a n d as a f u n c t i o n o f sample thickness. T h e calculations o f
F r a s i e r a n d Griffiths indicate that the infinite d e p t h approximation w i l l not be
v a l i d for nonabsorbing samples u n t i l the sample thickness approached 1 c m .

H o w e v e r , i f a sample does have i n f r a r e d absorption bands, k' w i l l decrease

the effective d e p t h o f penetration a n d , over the frequency region o f the
absorption, the infinite depth approximation m a y be valid f o r samples m u c h
less than 1 c m thick.
M a n d e l i s et a l . ( 2 5 ) d e r i v e d a treatment, based o n M e l a m e d ' s statistical
approach ( 2 6 ) , for calculating the diffuse reflectance a n d diffuse transmit-
tance o f powders w i t h a particle size that is very large w i t h respect to the
wavelength o f the incident radiation. G o o d agreement was obtained f o r
samples made u p o f particles w i t h (d) ~ 7k, w h e r e (d) is the average
particle diameter a n d λ is the wavelength o f the radiation; however, relatively

p o o r agreement was f o u n d f o r smaller particles, w h e r e the K M expression
becomes useful.
Polymer Studies Using DRIFT Spectroscopy

T h e r e are t w o different types o f p o l y m e r investigations that have b e e n
carried out w i t h D R I F T spectroscopy. T h e first type results f r o m the study o f
a p o l y m e r p o w d e r . I n this sort o f investigation, the considerations regarding
the sample itself are no different than those that w o u l d b e i n v o l v e d f o r a
typical organic analyte: particle size, sample homogeneity, a n d sample pack
ing. L e e et a l . ( 2 7 ) carried out just such a study o n complexes o f poly (vinyl
phenol) ( P V P h ) a n d p o l y ( 2 - v i n y l pyridine) ( P 2 V P ) . T h e complex precipitated
f r o m solution as a p o w d e r a n d gave very p o o r K B r pellet transmission spectra
due to the large amount o f scattering caused b y the analyte p o w d e r . U s i n g
D R I F T spectroscopy, these investigators were able to study the interactions
between the t w o species that comprise the complex; the spectra indicate the
formation o f a 1:1 complex. F i g u r e 3 shows the 2 2 0 0 - 3 8 0 0 - c m " region o f 1
the D R I F T spectrum o f a complex o f P V P h - P 2 V P , p u r e P V P h , a n d p u r e

P 2 V P . T h e two b r o a d , intense absorptions at 3525 a n d 3330 c m " f o r p u r e 1
P V P h are associated w i t h free a n d h y d r o g e n - b o n d e d O - H groups. T h e s e

bands are not present i n the complex; rather, a n e w b r o a d feature centered at
about 3000 c m " is apparent. T h i s n e w absorption is assigned to a strongly
1
p e r t u r b e d O - H vibration; the perturbation is caused b y interaction w i t h the

nitrogen atom o f the P 2 V P .
Siesler (28) used silica p o w d e r to m i m i c glass fibers a n d treated the
p o w d e r w i t h 7-propyltrimethyloxysilane, a c o u p l i n g agent u s e d to increase
reinforcement effectiveness i n fiber reinforced plastics. T h i s investigator was
able to m o n i t o r the decrease i n free O H (3740 c m " ) o n the glass surface
1
a n d the growth o f C H (2900 c m ) a n d C = 0 ( 1 7 0 0 - 1 7 2 5 c m " ) d u e to the

2
- 1 1
c o u p l i n g agent, as a f u n c t i o n o f the amount o f coating.

Savolahti ( 2 9 ) used D R I F T to study the t h e r m a l degradation o f barley
protein. T h e sample was l y o p h i l i z e d o r spray-dried. Samples w e r e m i x e d w i t h
K B r a n d heated i n a c o n t r o l l e d environment c e l l (from Spectra T e c h ) . Loss

3800 3000
Cm" 1
Figure 3. Scale-expanded DRIFT spectra in the range 3800 to 2200 cm ~ of 1
solid solutions in KCl (1:50 weight ratio): PVPh~P2VP polymer complex formed
with 4:1 initial composition (A); pure PVPh (B); and pure P2VP (C). (Reproduced
with permission from reference 27. Copyright 1984.)
o f the olefinic C - H stretch absorption was assigned t o oxidation o f the

double b o n d . T h e growth o f a strong C = 0 absorption b a n d was observed as
was the loss o f intensity associated w i t h O - H , N - H , C - H , a n d C - O groups.
T h e amide I and I I bands decreased at 1650 a n d 1540 c m , respectively. - 1
Polymer Fibers. T h e second type o f p o l y m e r investigation using

D R I F T spectroscopy is carried out w h e r e g r i n d i n g p o l y m e r fibers o r films
w o u l d change the chemistry a n d m o r p h o l o g y o f the system too drastically to
allow spectroscopic correlation o f the results w i t h the u n g r o u n d sample.
I n 1980, M a u l h a r d t a n d K u n a t h ( 3 0 ) used D R I F T spectroscopy w i t h
their o w n optical device a n d a c o m m e r c i a l F T I R to study a silane c o u p l i n g
agent o n glass fibers. C o n t r i b u t i o n s f r o m the C - H , C = 0 , a n d C = C v i b r a
tions o f the c o u p l i n g agent w e r e clearly seen, b u t useful i n f o r m a t i o n f o r
frequencies less than about 1500 c m - 1
was not obtained because o f the
strong i n f r a r e d absorptions o f the silica substrate.
Investigation o f c o u p l i n g agents o n glass fibers was o f interest to K o e n i g
a n d co-workers. A l t h o u g h m u c h o f their early w o r k was c o n d u c t e d using
transmission spectroscopy (31), K o e n i g a n d co-workers carried out a n u m b e r
o f investigations using D R I F T spectroscopy to study p o l y m e r fibers a n d films.

C u l l e r et a l . ( 6 ) characterized several o f the i n f r a r e d methods that m a y b e

used to obtain i n f r a r e d spectra o f polymers, i n c l u d i n g D R I F T spectroscopy,
and p o i n t e d out several o f the advantages a n d disadvantages o f D R I F T
spectroscopy. These advantages i n c l u d e g o o d sensitivity a n d little sample
preparation; the disadvantages i n c l u d e d the n e e d for a consistent particle size
for quantitative results, l i m i t e d d e p t h penetration, a n d that strongly absorbing
modes i n a material l i m i t the sensitivity o f the technique i n spectral regions
that those modes overlap. T h e authors r e p o r t e d initial spectra o f a c o u p l i n g
agent o n silica fibers that closely resembled those o f M a u l h a r d t a n d K u n a t h
(30).
I n 1984, the technique o f using K B r overlayers to obtain D R I F T spectra
o f p o l y m e r fibers was i n t r o d u c e d b y M c K e n z i e et a l . ( 3 2 ) , w h o investigated
the c o u p l i n g agent 7-aminopropyltriethoxysilane (7-APS) o n Ε-glass fibers.
Ε-glass fiber mats were cut into circles to fit the D R I F T spectroscopy cell.
H a d the samples obeyed the K u b e l k a - M u n k relation, it w o u l d have b e e n
possible to obtain the spectrum o f the c o u p l i n g agent o n the fibers b y
subtracting a spectrum o f the fibers alone f r o m that o f the fibers treated w i t h
7 - A P S . Unfortunately, this m e t h o d d i d not w o r k w e l l . Subtraction o f the
spectrum d u e to the Ε-glass substrate f r o m the spectrum o f Ε-glass treated
w i t h 7 - A P S y i e l d e d a spectrum i n w h i c h some o f the substrate bands h a d not
b e e n subtracted completely a n d some h a d b e e n oversubtracted. T h i s result
was an obvious indication o f n o n - K u b e l k a - M u n k behavior, presumably d u e
to anomalous dispersion. A n additional p r o b l e m that M c K e n z i e et al. e n c o u n
tered was that rotation o f the sample generated p r o f o u n d changes i n the
observed spectrum. A s i n their previous study (31) a n d the study b y M a u l
hardt a n d K u n a t h ( 3 0 ) , the useful range o f the D R I F T spectra was 4 0 0 0 - 1 6 0 0
c m . T h e lower l i m i t is a significant l i m i t a t i o n because it eliminates virtually
- 1
all o f what is typically referred to as the fingerprint region o f the i n f r a r e d

spectrum f r o m study. U s e o f a relatively t h i n (approximately 5 0 - m g ) layer o f
K B r o n top o f the sample scrambled the incident radiation a n d r e m o v e d the
observed rotational dependence o f the spectra, as w e l l as the apparent
contribution o f specular reflectance. Subtractions c o u l d b e carried out over
the range f r o m 4000 to 900 c m w i t h good e l i m i n a t i o n o f the Ε-glass bands
- 1
a n d w i t h clear spectral contributions f r o m the c o u p l i n g agent. T h e a d d e d

K B r r e d u c e d the spectral intensities o f all bands, b u t the r e d u c t i o n factor was
greater for the substrate than for the c o u p l i n g agent o n the surface o f the
fiber. M c K e n z i e et a l . postulate that the K B r overlayer m e t h o d makes the
incident a n d reflected radiation isotropic, w h i c h removes the orientational
dependence, a n d increases the average angle o f incidence o f the radiation to
the fibers, w h i c h causes greater reflection at the fiber surface a n d less
penetration into the fiber itself.
M c K e n z i e a n d K o e n i g ( 3 3 ) c o m p a r e d the use o f g r o u n d K B r overlayers
o n oriented fibers to the technique o f averaging several different sample
orientations ( 3 3 , 34) for obtaining D R I F T spectra o f glass fibers treated w i t h

a c o u p l i n g agent. E a c h orientation y i e l d e d a different spectrum, but averag

i n g several different sample orientations y i e l d e d linear K M plots as a f u n c t i o n
o f surface treatment. Unfortunately, the standard deviation o f the average
c o m p u t e d i n this way was as h i g h as 3 5 % , a n d the concentration breakpoint
corresponding to association o f the c o u p l i n g agent c o u l d not be d e t e r m i n e d .
M c K e n z i e a n d K o e n i g then u s e d coarse-ground ( 1 2 0 - 1 8 0 - μ π ι particle size)
K B r overlayers to remove the orientation dependence o f the observed
spectra. T h e overlayers r e d u c e d the intensity o f the observed bands b y about
a factor o f 2, b u t e l i m i n a t e d the orientation dependence o f the spectra a n d
enabled the use o f subtraction techniques to study the onset o f association o f

the c o u p l i n g agent.
B o t h D r i f t spectroscopy a n d photoacoustic spectroscopy ( P A S ) were u s e d
b y U r b a n et al. ( 9 ) to investigate stretching-induced phase transitions o f
p o l y ( b u t y l terephthalate) fibers a n d to characterize annealed and d r a w n

fibers. T h e spectra obtained using the two methods were similar; the P A S
studies h a d the a d d e d ability to characterize the orientation of surface
species. U s i n g D R I F T spectroscopy, the authors were able to characterize
the a l p h a - b e t a phase transition observed u p o n d r a w i n g the fibers a n d
observe the relaxation o f the fibers u p o n annealing.
C h a t z i et al. ( 3 5 ) used D R I F T spectroscopy w i t h the K B r overlayer
technique to study water absorbed i n polyamide fibers ( K e v l a r 49). U s e o f
gradually increasing amounts o f K B r as the overlayer demonstrated the loss o f
absorbed water due to a nitrogen purge as a f u n c t i o n o f d e p t h i n the p o l y m e r
fibers. T h e H 0 i n f r a r e d absorptions were characterized w i t h respect to the
2
nature o f the intermolecular interactions i n the polyamide fibers.
Polymer Films. C u l l e r et al. ( 3 6 ) u s e d the K B r overlayer technique

to study p o l y m e r films. T h e y investigated a m o d e l system consisting o f a
1.5-μ m poly (vinyl fluoride) ( P V F ) layer over a 2 9 ^ m - t h i c k substrate o f
poly(ethylene terephthalate) ( P E T ) . A d d i t i o n o f a surface layer o f K B r
increased the relative c o n t r i b u t i o n o f the P V F layer i n the spectra a n d
decreased the c o n t r i b u t i o n o f the P E T substrate. F i n e K B r p o w d e r (average
particle size less than 75 μ ι η ) h a d a m o r e dramatic effect than course p o w d e r
(average particle size 1 0 5 - 2 5 0 μ η ι ) . T h e authors suggest that the presence o f
the K B r overlayer increases the average angle o f incidence to the films a n d
increases the amount o f light reflected at the film interface, w h i c h makes the
technique m o r e sensitive to surface groups as K B r is added. T h e sensitivity o f
the m e t h o d to a very t h i n film o f a 7 - A P S c o u p l i n g agent o n P E T was also
demonstrated. T h e K B r overlayer technique brought out spectral c o n t r i b u
tions f r o m the c o u p l i n g agent, whereas the film o n P E T was transparent i n
transmission measurements. C u l l e r et al. postulate that the i n f r a r e d radiation
may make several reflections inside the thin-surface film i n this m e t h o d that
enhances the sensitivity o f the technique.

D R I F T spectroscopy was c o m p a r e d to attenuated total reflectance a n d

transmittance measurements b y C o l e et al. ( 3 7 ) for the study o f a c a r b o n -
epoxy composite consisting o f a w o v e n carbon fiber material impregnated
w i t h an epoxy resin. T h e sample was p r e p a r e d b y cutting the p r e p r e g
(fiber-reinforcement impregnated w i t h partially c u r e d resin) into 1 - c m X 1-
c m squares that were p l a c e d i n the sample c u p . A sulfone index a n d an
epoxide index were calculated f r o m the observed spectra, parameters that are
indicative o f t h e hardener to epoxy ratio a n d the degree o f polymerization,
respectively. T h e m e t h o d that gave the poorest results i n terms o f quantita
tive performance was D R I F T spectroscopy. Some o f the spectra clearly

showed the effects o f a large contribution f r o m F r e s n e l reflectance; that is,
the derivative-shaped bands d u e to the anomalous dispersion. Several differ
ent methods to reduce the F r e s n e l reflectance w i t h K B r overlayers were
attempted. A n opaque layer r e d u c e d the spectral contrast o f the spectra to

the extent that the m e t h o d c o u l d not b e used. T w o other methods were used
to generate very t h i n K B r overlayers, b o t h o f w h i c h increased the spectral
contrast a n d r e d u c e d the apparent contribution o f F r e s n e l reflectance, b u t
neither o f w h i c h i m p r o v e d the precision o f the measurements to any great
extent. T h e variation i n the thickness o f the surface resin layer, w h i c h
contributes to variations i n the F r e s n e l reflectance o f the samples, was
p r o p o s e d to b e the m a i n reason for the lack o f reproducibility. C o l e et a l .
only used one orientation to acquire the spectra: a n d orientation w i t h
approximately 8 0 % o f the fibers aligned w i t h the b e a m direction o f the
instrument.
C o l e et al. also used D R I F T spectroscopy to measure the degree o f
crystallinity o n the surface o f a composite material (38). A p r e p r e g (different
f r o m the one i n the foregoing study) that consisted o f a unidirectional
arrangement o f carbon fibers impregnated w i t h h i g h molecular weight
polyphenylene sulfide ( P P S ) was investigated. N o K B r overlayer a n d no
rotation o f the sample were used, a n d the orientation was w i t h carbon fibers
parallel to the b e a m direction o f the instrument. E x c e l l e n t spectra that
resembled spectra obtained w i t h transmission measurements were obtained.
T h e spectrum o f a sample w i t h l o w crystallinity was subtracted f r o m the
spectrum o f a sample w i t h h i g h crystallinity, a n d a pair o f peaks i n the
resulting difference spectrum, whose ratio changed significantly as a f u n c t i o n
of annealing, was d e t e r m i n e d . C o l e et a l obtained an excellent correlation
between the intensity ratio a n d the enthalpy o f crystallization f o r the p r e p r e g
that indicates that the intensity ratio is a good measure o f the crystalfinity o f
the composite.
Foams. C h a l m e r s a n d M a c k e n z i e ( 3 9 ) carried out a variety o f investi

gations a i m e d at illustrating the utility o f D R I F T spectroscopy for industrial
applications. O n e o f the m o r e interesting applications i n their study was the
use o f D R I F T spectroscopy f o r the study o f foams. F o a m s are sometimes

difficult to study by A T R because the pressure p l a c e d o n a f o a m sample is so

critical i n the A T R measurement. H o w e v e r , the D R I F T measurement was
easily carried out b y s i m p l y c u t t i n g the f o a m to the appropriate size, a n d the
identification o f a variety o f foams was demonstrated.
Catalytic Studies Using DRIFT Spectroscopy

H a m a d e h et al. (40, 41) w e r e the first to develop a heatable-evacuable c e l l
that c o u l d interface w i t h D R I F T optics. T h i s c e l l was u s e d to study the

i n f r a r e d absorption spectroscopy o f alumina-supported r h o d i u m clusters u n
der varying amounts o f C O , w h i c h represented different coverages. T h e
observed peaks i n the D R I F T spectrum w e r e assigned b y comparison o f the
D R I F T spectra w i t h previously assigned i n f r a r e d spectra o f r h o d i u m carbonyl

species. I n a recent extension o f these studies, V a n E v e r y a n d Griffiths (42)
obtained detection limits approaching 1 0 " monolayers o f C O adsorbed o n
6
alumina-supported r h o d i u m a n d observed that equilibration of the spectra

w i t h t i m e is a c o m p l i c a t i n g factor that depends o n the pressure o f C O to
w h i c h the catalyst is exposed. S m a l l amounts o f C O equilibrate relatively
rapidly o n the surface o f the catalyst whereas large amounts o f C O equilibrate
over l o n g times, presumably because this equilibration involves diffusion into
the pores o f the support. Baseline changes i n the spectra as a function o f the
pressure o f a d m i t t e d C O w e r e also observed a n d assigned to pressure-induced
changes i n the sample scattering coefficient. T h e results o f V a n E v e r y a n d
Griffiths i n d i c a t e d that m e r c u r y c a d m i u m telluride detectors are susceptible
to c o n d u c t i o n b a n d saturation effects w h e n hot samples are b e i n g observed,
an effect that w i l l lead to signal loss for high-temperature samples. T h e y
showed that deuterated triglycine sulfate or triglycine sulfate detectors do not
exhibit this susceptibility.
W i t h regard to using D R I F T spectroscopy as an i n situ technique, F i g u r e
4 is a schematic diagram o f an environmental c h a m b e r that has b e e n used i n
our laboratory to obtain i n situ D R I F T spectra. T h e c h a m b e r is similar i n
design to c o m m e r c i a l l y available cells, although most currently available cells
are m u c h more sophisticated i n design than the c e l l shown. T h e sample sits
o n top o f a post that can be heated v i a the cartridge heaters, a n d the
temperature o f the c e l l is m o n i t o r e d w i t h the t h e r m o c o u p l e . M o r e sophisti
cated designs call for a t h e r m o c o u p l e to b e p l a c e d directly i n contact w i t h the
sample, so that an accurate reading o f the sample temperature can be
obtained (43, 44). T h e cell allows for control o f the internal atmosphere,
either v a c u u m or a gas mixture, t h r o u g h connections to an external gas
m a n i f o l d a n d a v a c u u m p u m p . C o m m e r c i a l l y available cells allow for c o o l i n g
the section o f the c e l l containing the w i n d o w s , because the w i n d o w seals are
usually the l i m i t i n g consideration w i t h regard to the ultimate temperature
attainable. T h e flow p a t h o f any gases f r o m an external gas m a n i f o l d takes the

Figure 4. Schematic diagram of a DRIFT spectroscopy environmental chamber.
gases directly t h r o u g h the sample material. T h i s flow-through o f gases

compresses the p o w d e r to a certain extent, w h i c h gives rise to enhanced b a n d
intensities c o m p a r e d w i t h intensities observed without the flow. T h e samples
should not, however, be mechanically pressed to any great extent, because
compression prohibits gas flow through the sample (40). I n addition, after
flowing through the sample material, the gas stream can b e s a m p l e d b y gas
chromatography ( G C ) or gas chromatography-mass spectroscopy ( G C - M S ) ,
an application suggested b y H a m a d e h et al. (40) a n d i m p l e m e n t e d b y M a r o n i
et al. (43).
M a r t i n a n d Zabransky (45) studied various forms o f the zeolite Z S M - 5
( H - Z S M - 5 , F e - Z S M - 5 , a n d N a - Z S M - 5 ) a n d sihcalite for the conversion o f

m e t h a n o l to d i m e t h y l ether. T o study the adsorption process a n d products,

neat samples o f the zeolites i n a c o m m e r c i a l environmental chamber w e r e
used. Changes i n the O - H stretching region ( 3 5 0 0 - 3 7 5 0 c m ) that oc - 1
c u r r e d as methanol adsorbed o n the zeolites w e r e studied to determine w h i c h

sites w e r e b e i n g o c c u p i e d b y the m e t h a n o l as it adsorbed as a f u n c t i o n o f
temperature. A t r o o m temperature, adsorption o f methanol onto the zeolites
o c c u r r e d at only one O H site; at 150° C , two sites were i n v o l v e d for the active
zeolites H - Z S M - 5 a n d F e - Z S M - 5 , a n d o n l y one site is i n v o l v e d for
Na-ZSM-5.
M e t h a n o l fragmentation products w e r e studied b y observation o f the

infrared absorption pattern i n the C - H stretching region ( 2 7 0 0 - 3 1 0 0 c m ) . - 1
O n H - Z S M - 5 , adsorption o f m e t h a n o l gave rise to i n f r a r e d bands that c o u l d

be assigned to the methoxide group at r o o m temperature. A t higher tempera
ture (150 °C), the absorption pattern changed a n d the result c o u l d no longer
be i d e n t i f i e d as a methoxide. F e - Z S M - 5 gives the same sequence o f p r o d
ucts. M e t h a n o l adsorption o n N a - Z S M - 5 a n d silicalite resulted i n the f o r m a
tion o f the surface methoxide o n l y at r o o m temperature a n d at 200 °C.
T h o m p s o n a n d P a l m e r ( 2 2 ) u s e d i n situ D R I F T spectroscopy to study
the reaction o f S 0 w i t h C a C 0 . C a C O is u s e d as an adsorbent for S 0 i n
2 3 s 2
dry-injection flue gas cleanup systems. T h e evolution o f adsorbed S 0 as a 2
function o f t i m e a n d temperature f r o m sulfite to sulfate was investigated.

B a s e d o n their assignment o f the observed vibrational bands a n d o n their
previous i n f r a r e d photoacoustic measurements o n p u r e C a C 0 , T h o m p s o n 3
a n d P a l m e r p r o p o s e d a m e c h a n i s m for the adsorption o f S 0 a n d the 2
conversion of the physisorbed species to S 0 3

-
or S O f depending on
-
temperature.
O n e o f the limitations o f the D R I F T technique is the n e e d to dilute
strongly absorbing samples i n a nonabsorbing matrix to avoid reststrahlen
effects. I n their D R I F T studies, T h o m p s o n a n d P a l m e r u s e d N a C l as the
diluent (1:10 C a C 0 : N a C l ) , a n d i n their photoacoustic studies using p u r e
3
C a C O , bands that w e r e assigned to C a S 0 w e r e observed. These bands

s 2 3
w e r e not observed i n the D R I F T studies. Because N a C l , as w e l l as other

alkali additives, is k n o w n to accelerate the conversion o f C a S 0 to C a S 0 , 3 4
T h o m p s o n and P a l m e r point out that the n e e d to use the diluent i n the

D R I F T studies is potentially a very serious drawback, especially at elevated
temperatures.
M a r o n i a n d co-workers (43, 46, 47) studied a variety o f molecular sieve
catalysts b y using D R I F T spectroscopy. T o avoid problems associated w i t h
alkali halide diluents, p u r e zeolite materials w e r e used a n d regions o f the
spectrum that can show contributions f r o m reststrahlen effects ( w h i c h i n
cludes m u c h o f the region b e l o w 2000 c m for these types o f samples) w e r e
- 1
not investigated. Investigations w e r e l i m i t e d to the O - H a n d C - H (or O - D

and C - D ) stretching regions ( f r o m approximately 2000 to 4000 c m ) . - 1
Because m u c h o f the catalytic activity o f these zeolite catalysts is d e t e r m i n e d

b y the nature o f the acid sites, a significant amount o f i n f o r m a t i o n c o u l d be

obtained even w i t h this l i m i t a t i o n .
T h e differences i n the n u m b e r a n d type o f O - H sites were studied b y
M a r o n i a n d collaborators o n three different zeolites as a f u n c t i o n o f metal
atom substitution ( H - Z S M - 5 c o m p a r e d to A F S - H - Z S M - 5 , a ferrisilicate
zeolite) a n d as a f u n c t i o n o f aluminosilicate framework ( H - Z S M - 5 c o m p a r e d
to H - o f f r e t i t e ) . D R I F T spectroscopy w i t h subsequent gas c h r o m a t o g r a p h y -
mass spectrometry ( G C - M S ) was then used f o r determination o f products to
compare the reactivity o f the ferrisilicate zeolite A F S - H - Z S M - 5 a n d its
sodium exchanged f o r m A F S - N a - Z S M - 5 t o w a r d the conversion o f m e t h a n o l

to higher hydrocarbons as a function o f temperature a n d composition. T h e
experimental setup i n c l u d e d a provision f o r sampling the exhaust gases o f the
D R I F T environmental c h a m b e r w i t h a n on-line gas chromatograph a n d w i t h
a sample b u l b for G C - M S analysis. T h e sodium-exchanged forms were f o u n d

to b e 2 orders o f magnitude less reactive. T h e authors p o i n t out that probably
the most effective use o f the D R I F T technique i n i n situ measurements is
not as an absolute technique, b u t rather as a m o n i t o r o f changes that o c c u r as
a f u n c t i o n o f experimental variables. A D R I F T spectrum is obtained o f some
initial sample; t h e n this spectrum is subtracted f r o m subsequent spectra. T h e
set o f difference spectra shows changes i n the i n f r a r e d spectrum as a f u n c t i o n
o f t i m e , temperature, a n d reaction conditions i n a very clear way. A stacked
plot o f these spectra is a dramatic m e t h o d f o r showing spectroscopic changes
as a function o f the various experimental parameters.
M a r o n i a n d co-workers (46) used the same experimental arrangement to
study the formation o f Z S M - 5 f r o m the template t e t r a p r o p y l a m m o n i u m
cation ( T P A - Z S M - 5 ) a n d to study the reaction o f methanol, ethanol, a n d
ethylene o n H - Z S M - 5 f o r t h e formation o f higher hydrocarbons. U s i n g the
D R I F T technique i n conjunction w i t h on-line G C analysis o f reaction p r o d
ucts, the investigators were able to show that O H groups finking a l u m i n u m
a n d silicon atoms ( S i - O H - A l sites) are the sites at o r near w h i c h the alcohol
decomposition products adsorb, a n d that t e r m i n a l O H groups b o u n d to
silicon atoms ( S i O H sites) are labile b u t d o not appear to b e active i n the
catalysis. T h e shape o f the C - H stretch absorption d u e to the organic
fragment is indicative o f the activity o f the catalyst for a particular reactant.
A t temperatures Τ > 673 Κ, the reaction continues to generate products as
shown b y the G C results, b u t the surface-adsorbed species are not h e l d
tightly enough to r e m a i n o n the surface after a nitrogen purge. T h e onset o f a
b r o a d i n f r a r e d absorption i n the range 3 0 0 0 - 3 2 0 0 c m - 1
is attributed to
polycyclic aromatic coke precursors.
Iton et a l . (47) used D R I F T spectroscopy to examination the stabiliza
tion a n d redox chemistry o f C o (III) i n aluminophosphate zeolites. T h e y were
able to study the oxidation o f H 2 b y the stabilized C o (III) at elevated
temperatures t h r o u g h an increased O H absorption, a n d the 50 a n d 100 °C

oxidation of N O to N O +
b y C o (III) through the infrared absorption o f the
nitrosyl cation at 2162 c m - 1
a n d coordinated nitrosyl at 1674 a n d 1562 c m - 1
.
T h e species adsorbed o n a silver catalyst d u r i n g the oxidation of acetalde-
hyde was analyzed b y K a n n o a n d Kobayashi (48) using D R I F T spectroscopy.
T h e D R I F T spectra obtained f r o m the reaction were c o m p a r e d w i t h similar
spectra for silver salts, such as silver acetate, silver lactate, silver ketenide,
a n d silver carbonate. T h e s e comparisons, facilitated assignment of observed
peaks i n the i n f r a r e d spectrum o f the catalyst as b e i n g due to silver acetate
intermediates, a strongly adsorbed acetaldehyde, a n d an adsorbed alcohol.
T h e spectra obtained w i t h the D R I F T technique were c o m p a r e d w i t h spectra

for similar samples obtained b y transmission methods; the D R I F T m e t h o d
y i e l d e d m u c h better spectra i n the lower frequency region (1100 c m - 1
> v).
A l t h o u g h K a n n o a n d Kobayashi d i d dilute their catalyst samples i n K B r
d u r i n g the actual oxidation reactions, w h i c h w e r e c a r r i e d out at elevated

temperature (160 °C), they d i d not address the possibility of perturbation o f
the catalysis results due to the h i g h concentration o f alkali halide.
D R I F T spectroscopy was u s e d b y F r i e s a n d M i r a b e l l a (49) to study
commercial T i C l - A l C l
3 3 catalysts used i n the polymerization of propylene.
T h e y were able to m o n i t o r the decay o f the 1 6 4 0 - c m " absorption due to the
1
C=C group o f gas-phase propylene a n d the simultaneous growth of an

absorption at 1370 c m - 1
due to a m e t h y l deformation m o d e of polypropylene
o n the catalyst surface. T h e 1 8 2 0 - e m - 1
b a n d o f propylene, w h i c h corre
sponds to the first overtone o f the t e r m i n a l C H 2 wag, p r o v i d e d a m o r e
reliable measure o f the loss o f propylene d u e to the lack o f overlap b y other
spectral bands.
S m y r l a n d F u l l e r ( 5 0 ) u s e d i n situ diffuse reflectance spectroscopy to
examine the reactions o f neat coal samples. T h e s e authors point out that coal
samples n e e d no diluent to be studied b y D R I F T spectroscopy, because coal
effectively forms its o w n dispersion m e d i u m . B r i m m e r a n d Griffiths (24)
suggested a reason for this effect, based o n the idea that the coal particles
absorb so strongly that the effective penetration d e p t h is very small (on the
order o f 10 μ η ι ) so that a sample n o r m a l l y considered too strongly absorbing
to study b y D R I F T spectroscopy actually yields quite good spectra. V e r y
careful D R I F T investigations b y S m y r l a n d F u l l e r y i e l d e d well-resolved
spectra for the entire m i d - i n f r a r e d region. U s e o f the acetylation reaction as a
probe of the O H sites o n the coal a n d use o f the i n f r a r e d results to determine
exactly what types o f esters w e r e f o r m e d b y the acetylation allowed S m y r l a n d
F u l l e r to propose that the particular type o f coal u n d e r study contained only
phenolic-type O H groups a n d n o alkyl-type O H groups. T h e m e t h o d holds
m u c h promise for the study o f coal O H - s i t e distribution a n d coal chemistry i n
general.
T h e use of D R I F T spectroscopy for the study o f carbon-supported metal
catalysts, i n particular metal carbonyls, was explored b y V e n t e r et al. (44,

51-53). T h e i r initial investigations (44, 51, 52) focused o n the adsorption o f

F e ( C O ) , R u ( C O ) , and O s ( C O )
3 1 2 3 1 2 3 o n amorphous carbon black. T h e i r
1 2
studies investigated, i n a very careful manner, the effects o f a variety o f

experimental parameters o n the observed spectra, b o t h theoretically a n d
experimentally. T h e effects o f m e t a l loading, choice o f b a c k g r o u n d spectrum,
various forms o f baseline correction, and the diluent, b o t h the d i l u t i o n ratio
a n d the type o f diluent, w e r e observed and the linearity o f the K u b e l k a - M u n k
transform of the data for a range o f metal loadings o n these carbon-supported
samples was established. T h i s range d e p e n d e d o n the d i l u t i o n ratio, a n d the
choice o f d i l u t i o n ratio i n v o l v e d a c o m p r o m i s e between detection limitations

and linearity o f the transformed data. T h e final choice for d i l u t i o n ratio was
1:200 b y weight for carbon-supported catalyst to diluent. T h e choice for the
diluent itself was a c o m p r o m i s e between the effect o f the diluent o n the
observed chemistry a n d the effect o n the observed spectroscopy. A l O a n d 2 s
S i 0 h a d the least effect o n the chemistry but t e n d e d to adsorb water, w h i c h

2
caused baseline drifts i n the spectra a n d made the spectra h a r d to interpret.

Ultimately, C a F was chosen as the diluent.
2
T h e choice o f material to generate the b a c k g r o u n d spectrum also af

fected the final K u b e l k a - M u n k spectra. Rather than use a nonabsorbing
sample (i.e., p u r e diluent) as the b a c k g r o u n d " s a m p l e " , V e n t e r et al. used a
sample consisting o f decarbonylated carbon black i n the appropriate ratio,
1:200, i n the diluent. T h u s , the K u b e l k a - M u n k spectra w e r e calculated
relative to a b a c k g r o u n d that absorbed radiation at the same frequencies as
the catalyst support. T h i s b a c k g r o u n d was not expected to have any effect o n
the linearity o f the K M intensities for the bands due to the adsorbed
C O - c o n t a i n i n g species, a n d the use o f this material to generate the back
g r o u n d spectrum y i e l d e d m u c h better signal-to-noise ratios a n d better base
line correction.
I n later investigations, V e n t e r et al. (53) used the technique d e m
onstrated i n earlier studies to examine the t h e r m a l decomposition o f
five different metal carbonyls o n carbon: F e ( C O ) , N E t [ F e M n ( C o ) ] ,
3 1 2 4 2 1 2
M n ( C O ) , K [ H F e ( C O ) ] , a n d K [ F e M n ( C O ) ] . D R I F T spectroscopy
2 1 0 3 n 2 1 2
alone was used to measure the rate constant for decarbonylation as a f u n c t i o n

o f temperature a n d to calculate the activation energy o f decarbonylation for
these five carbon-supported species u n d e r H e a n d H . T h e decomposition 2
kinetics o f all o f the species f o l l o w e d first-order kinetics, a n d the rates as a

function o f temperature w e r e fitted w e l l w i t h the A r r h e n i u s expression. T h e
Fe (CO)
3 clusters w e r e the least stable, w i t h rate constants for decomposi
1 2
tion o f about 1 m i n a n d E values o f 7 5 - 8 8 k j / m o l . M n ( C O )

- 1
A p r o v e d to
2 1 0
be the most stable c o m p o u n d w i t h decomposition rate constants o f approxi

mately 0.001 m i n at 350 Κ a n d activation energy E
- 1
values for the A
decomposition o f 1 3 4 - 1 5 5 k j / m o l . T h e decomposition routes o f the M n -

containing clusters w e r e f o u n d to d e p e n d o n the atmosphere u n d e r w h i c h the
decomposition took place.

NAVENUMBER
Figure 5. Evolution of the DRIFT spectrum of supported Cu(acac), as a

function of metal loading. The lowest spectrum is that of a 0.92% wt/wt Cu
sample on Si0 (Cab-O-Sil). The spectra of six different metal loadings are
2
shown in sequence from bottom to top representing metal loadings of 0.92, 1.7,
2.5, 3.8, 4.5, and 5.6% Cu on Si0 , respectively.
2
A l l o f the foregoing data was generated b y studying the i n f r a r e d absorp

tion o f the C O species, n o m i n a l l y 1 9 0 0 - 2 1 0 0 c m . T h e region o f C H
- 1
stretch absorption y i e l d e d some i n f o r m a t i o n c o n c e r n i n g the types o f products

that might b e expected. T h e K - c o n t a i n i n g catalysts showed significantly
greater i n f r a r e d absorption d u e to C H (as opposed to C H ) groups, p r e s u m
2 3
ably o n the support surface. T h i s i n f o r m a t i o n is consistent w i t h earlier

observations that the presence o f potassium promotes chain growth i n the
products o f the syngas reaction.
K e n v i n a n d co-workers (54-56) showed that D R I F T spectroscopy is very
useful for the study o f supported catalyst precursors o n oxide surfaces. T h e i r
study o f C u ( a c a c ) o n S i 0 demonstrated that the D R I F T technique c o u l d
2 2
be used to show the onset o f multilayer formation o f the supported complex

a n d that subtraction o f K M plots o f the first-layer species f r o m spectra o f
samples that h a d m u l t i p l e layers o f C u ( a c a c ) o n the silica surface y i e l d e d a
2
spectrum o f the overlayers; that is, the C u ( a c a c ) species not i n direct contact
2
w i t h the silica surface. F i g u r e 5 shows a spectrum o f the impregnated silica

p o w d e r as a f u n c t i o n o f metal loading. T h e onset o f the absorption at 1552
c m " is thought to indicate the presence o f m u l t i p l e layers o f C u ( a c a c ) o n
1
2
the silica surface. F i g u r e 6 is a spectrum that results f r o m a subtraction o f a

less-than-a-monolayer spectrum f r o m a spectrum o f a sample containing

m o r e than o n e monolayer o f complex. T h e result is i n remarkably g o o d

agreement w i t h that o f p u r e C u ( a c a c ) 2 as shown i n F i g u r e 7. K e n v i n (55)
a p p l i e d the D R I F T technique to the study o f a variety o f similar complexes,
including Pd(acac) , Pt(acac) , and Cr(acac) . T h e palladium and platinum
2 2 3
complexes showed behavior similar to that shown b y the copper system,

although less adsorption for these complexes was observed. T h e c h r o m i u m
complex showed very little adsorption a n d n o spectral changes f o r the
material that d i d adsorb, w h i c h might b e expected f o r the octahedral
complex.
Summary
D i f f u s e reflectance spectroscopy i n the m i d - i n f r a r e d range is a p o w e r f u l
technique for the study o f certain types o f samples, i n c l u d i n g polymers,
heterogeneous catalysts, a n d n o v e l materials. D R I F T has great potential f o r
the study o f a w i d e variety o f processing p r o b l e m s a n d for i n situ investiga
tions, b o t h as a stand-alone technique a n d i n conjunction w i t h G C a n d
G C - M S . W h a t must b e kept i n m i n d i f useful results are expected are the
approximations inherent i n the technique such as optically dilute samples, the
problems a n d the solutions associated w i t h specular a n d diffuse Fresnel
reflectance, a n d the n e e d f o r reproducible sample preparation.

References
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RECEIVED for review July 15, 1991. ACCEPTED revised manuscript September
25, 1992.


1993 Mitchell Drift

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13

Fundamentals and Applications

Transform (DRIFT) Spectroscopy

Department of Chemistry, Clark Atlanta University, Atlanta, G A 30314

Diffuse reflectance spectroscopy is a powerful tool for the study of

DIFFUSE REFLECTANCE INFRARED FOURIER TRANSFORM (DRIFT) spec­

In Structure-Property Relations in Polymers; Urban, M., et al.;

sample into a transparent pellet. T h i s preparation can easily result i n irre­

govern diffuse reflectance spectroscopy were d e t e r m i n e d as a result o f

In Structure-Property Relations in Polymers; Urban, M., et al.;

Attenuated total reflectance ( A T R ) is one o f the best ways to obtain

absorbing or highly reflective samples. A n o t h e r general conclusion is that

rubbers, for example, because it is difficult to control particle size f o r a

Optical Constants. T h e intensive property that characterizes t h e

component) a n d the absorption index (k ) (called the imaginary component):

F o r nonabsorbing materials, k' = 0. Specularly reflected light is w e l l d e ­

In Structure-Property Relations in Polymers; Urban, M., et al.;

l e a d to reflection can be due to differences i n the real o r the imaginary

w h e r e k is the absorption coefficient (Φ k') a n d χ is the path length t h r o u g h

w h e r e ν is the frequency o f the radiation (per centimeter) a n d the absorption

coefficient is related to the absorptivity, a, a n d the concentration, c, o f a n

Kubelka-Munk Expression. I n any spectroscopic technique it is

w h e r e R is the absolute reflectance o f an " i n f i n i t e l y t h i c k " sample,

represents the value o f the K u b e l k a - M u n k f u n c t i o n , k is the absorption

It is generally assumed that s is a constant or at most a slowly varying

In Structure-Property Relations in Polymers; Urban, M., et al.;

because the effective path length increases b y a factor o f 2 f o r diffuse

R (sample) is the reflectance o f the sample a n d R (standard) is the

reflectance o f a nonabsorbing standard, such as K B r o r K C l . F o r samples that

Fresnel Reflection. T o a i d a discussion o f several o f the causes a n d

In Structure-Property Relations in Polymers; Urban, M., et al.;

Figure 1. Schematic diagram of the DRIFT interaction with three classes of

at an angle that is equal to the angle o f incidence at t h e grain interface, yet

In Structure-Property Relations in Polymers; Urban, M., et al.;

spectroscopy. Specular F r e s n e l reflectance is relatively easy to eliminate f r o m

fraction o f incident radiation that is reflected out o f the sample without b e i n g

observed spectrum can be characterized using the K u b e l k a - M u n k relation.

absorption b a n d , the index o f refraction fluctuates rapidly as a f u n c t i o n o f

tion indices o n the order o f 1.5 (21). T h e weakly absorbing C - H stretch

Optical Accessories. Several companies manufacture optical acces­

In Structure-Property Relations in Polymers; Urban, M., et al.;

Radiation from To detector

In Structure-Property Relations in Polymers; Urban, M., et al.;

Comparisons o f these two configurations have b e e n carried out b y at least

Sample Preparation. O n e o f the limitations o f diffuse reflectance

the reproducibility o f the technique. Because the sample materials are

In Structure-Property Relations in Polymers; Urban, M., et al.;

process. I n general, pressure increases the spectral contrast o f the observed

T h e effect o f using infrared-absorbing materials as diluents was investi­

the considerations that B r i m m e r a n d Griffiths discuss are applicable. I n situ

f u n c t i o n o f frequency (although b y n o m o r e than about a factor o f 2 over the

In Structure-Property Relations in Polymers; Urban, M., et al.;

H o w e v e r , i f a sample does have i n f r a r e d absorption bands, k' w i l l decrease

particle diameter a n d λ is the wavelength o f the radiation; however, relatively

Polymer Studies Using DRIFT Spectroscopy

the D R I F T spectrum o f a complex o f P V P h - P 2 V P , p u r e P V P h , a n d p u r e

P V P h are associated w i t h free a n d h y d r o g e n - b o n d e d O - H groups. T h e s e

p e r t u r b e d O - H vibration; the perturbation is caused b y interaction w i t h the

a n d the growth o f C H (2900 c m ) a n d C = 0 ( 1 7 0 0 - 1 7 2 5 c m " ) d u e to the

c o u p l i n g agent, as a f u n c t i o n o f the amount o f coating.

In Structure-Property Relations in Polymers; Urban, M., et al.;

Figure 3. Scale-expanded DRIFT spectra in the range 3800 to 2200 cm ~ of 1

o f the olefinic C - H stretch absorption was assigned t o oxidation o f the

DIFFUSE REFLECTANCE INFRARED FOURIER TRANSFORM (DRIFT) spec

sample into a transparent pellet. T h i s preparation can easily result i n irre

F o r nonabsorbing materials, k' = 0. Specularly reflected light is w e l l d e

Optical Accessories. Several companies manufacture optical acces

T h e effect o f using infrared-absorbing materials as diluents was investi

a c o u p l i n g agent. E a c h orientation y i e l d e d a different spectrum, but averag

Foams. C h a l m e r s a n d M a c k e n z i e ( 3 9 ) carried out a variety o f investi

T h e choice o f material to generate the b a c k g r o u n d spectrum also af

be the most stable c o m p o u n d w i t h decomposition rate constants o f approxi

A l l o f the foregoing data was generated b y studying the i n f r a r e d absorp