1470 ANALYTICAL CHEMISTRY, VOL. 51, NO.
9, AUGUST 1979
volume cell could conceivably provide a factor of 1000 im-
provement in this minimum detectable quantity. Amplitude
measurements afford the possibility of measuring molecular
weights directly at the output of the GC column, since am-
plitude response is a function of molecular weight. Improved
sensitivity, especially for high molecular weight compounds,
could easily rank the SAW device with thermal conductivity
and flame ionization type GC detectors. The prospects for
improving the amplitude measurement scheme are quite good
when one considers that the system noise level is presently
about four orders of magnitude greater than the theoretical
noise level generated by the detector itself.
Compared to existing GC detectors, the lithium niobate
SAW device is not presently competitive in terms of sensi-
tivity, linearity, or dynamic range. A conventional thermal
conductivity cell could probably do a factor of 10 better with
little difficulty (3). In addition a thermal conductivity detector
has a linear range of about 10' compared to about 10' for the
SAW device. The sensitivity of the SAW device could be
improved by operation a t higher frequencies. The linearity
could be improved slightly with an electronic oscillator that
was less amplitude sensitive.
Surface Acoustic Wave Probes for Chemical Analysis. 111.
Thsrmomechanical Polymer Analyzer
Henry Wohltjen' and Raymond Dessy"
Chemistry Department, Virginia Polytechnic Institute and State University, Blacksburg, Virginia 2406 1
A surface acoustic wave device was developed to perform
thermomechanical analysis of polymer films. Amplitude
measurements of TBfor polycarbonate, polysulfone, and single
and twephase copolymers of the above agree with Rheovibron
measurements. Low order transitions (at 24 "C) have been
measured in Teflon. Although the T, measurements using SAW
devices were made at 30 MHz, the poor coupling with the
surface made by normal disk samples resulted in the excellent
agreement observed with classical low frequency methods.
On the other hand, cast films, which have good surface contact
with the substrate, show the shifts in T , predicted by the
time-temperature principle.
T h e attenuation of the amplitude of a Rayleigh wave
propagating in a quartz SAU' delay line has been used to
determine the glass transition temperature of polymer films
clamped to the surface. Agreement with low frequency
dynamic mechanical measurements on the same films is good.
The attenuation is a result of changes in the surface contact
between the polymer film and the SAW device which occur
when the elastic modulus of the polymer decreases a t the glass
transition temperature. Measurements obtained by this
measurement are not reversible.
A crystalline transition occurring in Teflon was easily
detected in a specimen clamped t o the SAW device. At-
tenuation of the surface wave was a consequence of the surface
Present address: IBM Watson Research Laboratory, Yorktoan
Heights, N.Y.
0003-2700/79/0351-1470$01 OO/O
The SAW device GC detector does have some properties
that continue to make it interesting. It is nondestructive and
can theoretically be used with any carrier gas. The cost of
the detector and electronics is low and it is possible to make
the detector specific by the application of a selective coating.
ACKNOWLEDGMENT
The authors thank H. M. McNair for advice and consul-
tation on the chromatographic aspects of this research.
LITERATURE CITED
(1) Famell, G. W. "SAW Propagationm Piezoe!ecVic %W', Wave€k3mks,
1976, 2, 15.
(2) King, W. H. "Using Quartz Crystals as Sorption Detectors . . . Parts 1
& 2 " , Res.lDev. 1969, 20(4 8 5), 28.
(3) Hartmann, C. H. "Gas Chromatography Detectors," Anal. Chem. 1971,
4 3 ( 2 ) , 113A.
RECEIVED for review January 22,1979. Accepted May 1,1979.
The authors thank the Gillette Charitable and Educational
Foundation whose funds helped support this research, and
Bendix Corpoation for the loan of a Model 2200 Gas Chro-
matograph. All plots were made on a Benson Lehner Plotter,
a gift from Corning.
contact increasing as the sample expanded. The transition
is characterized by a significant change in the coefficient of
linear expansion of Teflon. Observations of this transition
are reversible.
A cast film is mechanically coupled to the surface wave.
Under these conditions, the measured glass transition tem-
perature, T g ,is observed to be much higher than that found
in experiments conducted a t low frequencies, as theory
predicts. Measurements of the cast film properties are re-
versible.
The utility of the SAW device in photoresist investigations
has been demonstrated by monitoring the effects of solvent
evaporation and photo induced cross-linking of the resist. The
device affords a significant advantage in studies of this kind
because it can monitor films of the same thickness used in
industrial applications.
The SAW device will undoubtedly find many other ap-
plications in polymer analysis where its high sensitivity and
ability to handle small samples are essential.
EXPERIMENTAL
A quartz SAW device was employed in all studies of the thermal
behavior of polymer films in contact with the surface. The
previously described temperature test apparatus ( I ) was used to
provide temperature control over the range of 0 to 200 "C. The
polymer films required a clamping mechanism to provide a re-
producible contact force. The system shown in Figure 1 was the
most effective. Owing to the very large attenuation of the surface
wave amplitude which was produced by a polymer film a t its glass
transition temperature, a modified amplitude measurement system
was used. The sensitive balanced bridge system described
previously was replaced by a much simpler apparatus shown in
Figure 2 . The size of the polymer samples was kept small to
F 1979 American Chemical Society
 ANALYTICAL CHEMISTRY, VOL. 51, NO. 9, AUGUST 1979 1471

RELEASE
%.
0
-1
B

I
w 2 J 0
0

8!
c

li:
I
u1

0 I IO" I I o]
N

IJLL L
+-- 0
F l O ' - - ) i
END VIEW
25 ___c/
SIDE V I F W
0
0
I
30
I
60 30
I
120
I
150
Figure 1. Polymer film clamping system TEMPERRTURE (DEGREES C)

Figure 3. Polyethylene terephthalate glass transition profile

D
0

-1
DC VOLTAGE LEVEL
* TOLSI.11

Figure 2. Simplified amplitude measurement apparatus

prevent excessive attenuation of the wave. Samples were '/s-in.
in diameter and were obtained by using an ordinary paper punch.
The polymers were pressed into films about 10 mils thick.
After mounting the 1/8-in.diameter film on the surface of the
SAW device, the rf power level and rf amplifier output tuning
controls were adjusted to provide about 9.5 V of dc signal as
measured at the output of the detector amplifier. The temperature
scans in all experiments were done in increments of 3 "C at a rate
of 1.5 OC/min.
The bisphenol A polycarbonate homopolymer film was 10 mils
thick and had a number average molecular weight (M,) of about
15000. An oriented sample was obtained by straining it 50% in
a tensile test apparatus. The thickness of this oriented bisphenol
A polycarbonate sample was 7 mils. The polysulfone homo-
polymer film was originally 10 mils thick and had a molecular
weight (M,) about 28 000. An oriented polysulfone sample had
a thickness of 8 mils and was obtained by straining it 25% in a
tensile tester. Single- and two-phase block copolymers of the
polysulfone and polycarbonate were also tested. The single-phase
block copolymer had blocks of polycarbonate (M, = 10 000) and
polysulfone (M, = 10000) combined to give a molecular weight
(M,) of about 36 000. The single-phase block copolymer films
were 14 mils thick. A two-phase block copolymer was tested which
was made from blocks of polycarbonate ( M , = 22 000) and poly-
sulfone ( M , = 26 000) to yield a product with a molecular weight
(M,) of about 40000. Films of the two-phase copolymer were 14
mils thick. The classical glass transition temperatures (T,) were
measured on a Rheovibron dynamic mechanical tester operating
a t 3.5 Hz.
An attempt was made to detect a well known crystalline
transition occurring in poly(tetrafluoroethy1ene) around room
temperature. A 25-mil thick sample of Teflon sheet was obtained
and a '/8-in. diameter sample was clamped onto the surface and
cycled between 0 and 60 "C in search of the transition.
An experiment was conducted to see if the mechanical behavior
of very thin polymer films cast upon the surface could be
monitored. A 0.2-g piece of poly(methy1 methacrylate) was
dissolved in 20 mL of acetone. A single drop of this solution was
placed on the SAW device and the solvent was permitted to
evaporate. The temperature of the film was scanned from 60 to
180 "C.
Current interest in polymer photoresists and their behavior
inspired a series of experiments to ascertain if the rate of solvent
evaporation and rate of photo irradiation induced cross-linking
could be followed using the SAW detector. Kodak KPR pho-
toresist was mixed 1 part to 2 with Kodak KPR Thinner. A drop
- 1
,
*sa......
I 1
0
0 40 BO
1 I
120 160 200
TEMPERRTURE (DEGREES C)
Figure 4. Bisphenol A polycarbonate (unstrained) glass transkion profile
of this solution was applied, under subdued lighting conditions,
to the surface of the SAW device and the amplitude response was
monitored at room temperature. When the solvent was completely
evaporated, a small UV lamp was used to illuminate the pho-
toresist. The response of the SAW device amplitude was recorded.
RESULTS
A 10-mil thick film of polyethylene terephthalate produced
the curve shown in Figure 3. As the temperature approached
the glass transition, the sample began to soften and adhere
to the SAW device, thus attenuating the wave. At 75 "C the
wave was almost completely attenuated. This is the reported
glass transition temperature of polyethylene terephthalate.
Thus, points of discontinuity in the amplitude vs. temperature
profiles provide a clear indication of the glass transition
temperature of polymer specimens clamped t o the SAW
device.
Figure 4 presents the results of a n unoriented bisphenol
A polycarbonate sample. A glass transition temperature of
156 "C is apparent. Another polycarbonate sample was
strained by 50% and the resulting profile appears in Figure
5. The results are very similar with the strained sample,
indicating a T , of 152 "C.
Figures 6 and 7 show the amplitude vs. temperature re-
sponse of an unoriented polysulfone film and one strained by
25%. Once again, the results are quite similar with the T ,
of the unoriented sample occurring a t 186 "C and that of the
1472 ANALYTICAL CHEMISTRY, VOL. 51, NO. 9, AUGUST 1979

0
0
d

N
J0 Z
c

rn
>
5 0
Ln
c
Y
L
ln

w o
0 -
2
I

e
J

a .
N
B o N

-....e.... ......
0 4 I I I 1 0 I I I I 1
40 ao 120 160 200
TEMPERRTURE (OEGREES C)

Figure 8. Single-phase block copolymer glass transition profile

0
.....
7

...*
0 I I I I 1 -0I 40 8'0 120 160 200
TEWPERRTURE (DEGREES C )

Figure 9. Two-phase block copolymer glass transition profile

Table I. Comparison of Tg Measurement Methods

Glass Transition
Temperature, 'C
SAW
polymer Rheovibron device
polycarbonate 150 156
polysulfone 190 186
polycarb-polysulfone, 175 174
single-phase copolymer
polycarb-polysulfone, Tgl= 1 6 0 ' C 171
two-phase copolymer Tp,= 1 8 1 ^ C 195

Two discontinuities appear in the profile at 171 and 195 "C

which correspond to the Tg'sof the two domains present in
the film. Interpretation of the data at temperatures above
100 "C was made difficult by the temperature dependence of
the transducer efficiency. A large base-line shift is actually
O I I I I I
0 40 ao 120 160 200 superimposed on the profiles in Figure 4 through 9. It should
TEWPERRTURE (OEGREES C) be possible to design interdigital transducers for the SAW
Figure 7. Polysulfone (strained 25 % ) glass transition profile device which minimize this base-line shift with temperature.
Comparison T , measurements were performed on a
strained sample occurring at 189 "C. Rheovibron dynamic mechanical analyzer operating a t 3.5 Hz.
The glass transition for a single-phase polycarbonate- Table I lists the results obtained by measuring tan delta peaks
polysulfone copolymer is presented in Figure 8. A single T , on the Rheovibron and results obtained from the SAW device.
of 174 "C is indicated. Figure 9 illustrates the results obtained An experiment was performed to see if the subtle crystalline
from a two-phase polycarbonate-polysulfone block copolymer. transition of Teflon could be detected around room tem-
 ANALYTICAL CHEMISTRY, VOL. 51, NO. 9, AUGUST 1979 1473
0

'a

J
a

0
YI,
I I I 1 I
0 1 I I I I I
0 10 20 30 40 50
TIME (SEC) *lo-*
Figure 10. Teflon crystalline transition
Figure 12. Solvent evaporation in KPR photoresist
0
0

-1
7
..........a
N

.
0
r(

c
5
t
c
k
X
u)

r
=
N
o
..**I .
W
0
2
I

l-I
l

s =i
'1 I
4
UVON

0 I 0
t
0 *O an 120 160 250 4 I I I I

TEMPERRTURE (OEGREES C)

Flgure 11. Glass transition profile of a PMMA cast film

perature. The results are presented in Figure 10. A sub-

stantial signal was obtained with maximum attenuation of the
surface wave occurring at a temperature of 27 O C , in agreement
with the literature.
All of the studies conducted up to this point utilized
polymer film specimens about 10 mils thick. A very thin film
of poly(methy1 methacrylate) (PMMA) was cast as described
in the Experimental section. This film contained about 200
gg of the polymer and covered a circular area on the SAW
device which was about 9 mm in diameter. The thin film had
a thickness of approximately 0.1 mil. No clamp was used on
this specimen. The amplitude response vs. temperature profile
for the PMMA film is displayed in Figure 11. A very strong
attenuation of the surface wave was observed with the peak
attenuation occurring a t a temperature of 150 "C. Figure 12
illustrates the response of the SAW device as solvent evap-
orates from a spot of KPR photoresist present on the surface.
The effect of then irradiating this photoresist film is shown
in Figure 13. The sudden shift in the base line after 200 s
is caused by electronic interference when the UV lamp is
turned on. A steady decrease in the attenuation is observed
until approximately 300 s has elapsed, a t which time the
irradiation ceases to have a significant effect on the film.
DISCUSSION
The interesting mechanical properties of polymers are a
direct consequence of the fact that they are viscoelastic
1474 0 ANALYTICAL CHEMISTRY, VOL. 51, NO. 9, AUGUST 1979
perimentally cannot be explained so simply. First of all, the
loss modulus for a linearly viscoelastic material experiences
a maximum at or near the glass transition temperature (2).
The Tgp.rofiles obtained from the SAW device do not exhibit
any maxima (or minima) when the sample is clamped to the
SAW device. Instead, complete attenuation of the surface
wave persists long after the glass transition temperature has
been passed. An explanation for the glass transition behavior
of thick film (i.e., 10 mils) polymer specimens mechanically
clamped to the surface can be realized if one considers the
following: First, the loss modulus of the sample is large enough
to cause substantial attenuation of the surface wave even when
the sample is nowhere near the glass transition temperature.
Second, the only factor preventing complete attenuation of
the wave prior to reaching the glass transition temperature
is the relatively poor adhesion of the polymer in the SAW
device. The films used were not optically flat and this would
be essential if good adhesion to the surface was to be obtained.
Third, as the glass transition temperature was reached, the
polymer would soften and the clamp would press it into more
intimate contact with the SAW device. Thus, the adhesion
would be increased and the wave would be greatly attenuated.
There is additional evidence to support this hypothesis.
T h e T , profiles of polymer films clamped to the surface were
not reversible. T h a t is, if the sample was cooled down far
below the glass transition temperature, the large surface wave
attenuation would remain. (Cooling the film would not make
the surface rough again.) Further support of the hypothesis
can be obtained by considering the time-temperature su-
perposition principle (3). Essentially, this principle states that
the temperature at which a polymer transition occurs is
frequency dependent. Dynamic mechanical test systems
usually excite a periodically varying strain in the polymer and
monitor the stress produced. The frequency of the strain
commonly falls in the range of to lo3 Hz. Glass transition
temperatures which are measured dynamically exhibit a
frequency dependence. The SAW device was exciting strain
oscillations at a frequency of approximately 3 X lo7 Hz. The
time-temperature superposition principle predicts very large
shifts in the observed TB'sfor the polymers studied. But the
glass transition temperature measurements experimentally
obtained show very good agreement with low frequency
dynamic measurements. This is proof that the adhesion of
the mechanically clamped polymer was not adequate for
coupling to the surface wave to occur, otherwise the exper-
imentally observed T i s would have occurred at substantially
higher temperatures. The SAW device is not making a dy-
namic mechanical measurement on polymer films clamped
to the surface. Rather, the SAW device is monitoring changes
in surface contact. As the glass transition temperature is
approached, the storage modulus (G,) decreases permitting
better surface contact owing to the reduction in polymer
elasticity. The increased surface contact leads to a large
attenuation of the surface wave from compressional wave
energy loss into the polymer film.
The comparison illustrated in Table I shows relatively small
differences between the Rheovibron and the SAW device. It
should be understood that a number of methods exist for
determining polymer glass transition temperatures. These
include DTA, DSC, TMA, dilatometry, and, of course, dy-
namic mechanical methods ( 4 ) . Each method requires in-
terpretation to determine the glass transition temperature.
For this reason, exact agreement between measurement
techniques is frequently not obtained.
There are several factors which distinguish the SAW device
as a useful monitor of polymer glass transitions. The device
is very sensitive and this permits very small samples to be
used. Sample preparations and mounting are absolutely
trivial. The device is quite rugged and possesses a small
thermal mass which permits fairly rapid-temperature scans
to be made.
While T , measurements are very useful, the ability of the
SAW device to detect more subtle transitions would greatly
increase the spectrum of potential applications. Most
polymers experience relaxation transitions a t temperatures
far below the glass transition. These relaxations typically
involve movements of small chain segments or side groups and
exhibit modulus changes substantially less than those seen
at the T,. Poly(tetrafluoroethy1ene) (Teflon) undergoes a
first-order transition around room temperature which is a
result of order-disorder effects in the crystalline regions of
the polymer (5). The response obtained from the SAW device
with a Teflon film on the surface (Figure 10) agrees very
closely with data describing the linear expansion coefficient
of Teflon (6). Between 10 and 27 "C, the Teflon linear ex-
pansion coefficiencincreases from about 1.25 X to 2.1 X
reciprocal degrees centigrade. This would cause the film
to swell slightly on the surface, thus increasing the surface
contact which results in greater attenuation of the surface
wave. The phenomenon was reversible and reproducible, as
one would expect. Thus, the SAW detector seems very well
suited as a sensitive monitor of expansion coefficient changes
associated with subtle polymer mechanical transitions.
The results of casting a poly(methy1 methacrylate) film on
the surface were very revealing. It was surprising that the
presence of such a small amount of polymer could produce
such a large interaction with the surface wave. The thickness
of the film (about 0.1 mil) was significantly less than the
wavelength of the surface wave (4 mils). This demonstrates
that the surface wave interaction does not extend very far into
the adjacent layer. The most striking result, however, was
the temperature at which the PMMA film exhibited its glass
transition. Conventional, low frequency measurements in-
dicate that the T, of PMMA is in the vicinity of 100 OC. The
SAW device indicated a T , of 150 "C. This large shift is
consistent with the time-temperature superposition principle.
It, therefore, appears that the cast film was indeed coupled
to the propagating surface wave. An additional significant
feature of the profile shown in Figure 11 is that a minimum
occurs. This represents a maximum in the energy loss caused
by the modulus ( 2 ) . Experiments with the PMMA cast film
indicated that the phenomenon was reversible and repro-
ducible. It is obvious then, that the dynamic mechanical
measurements can be performed on very small polymer films
cast on the surface of a SAW device.
The final application of the SAW device was in the area
of photoresist materials. Solvent evaporation rate during the
baking of the photoresist can have a significant effect on the
quality of the film ( 7 ) . The use of a SAW device permits
investigations of this rate to be conducted with films that are
the same thickness as those used in practice. Presently
available techniques which employ microbalance monitoring
of bulk photo resists do not provide direct information about
film behavior (8). The effect of placing a drop of KPR
photo-resist on the surface is shown in Figure 12. Wild os-
cillations experienced shortly after application of the liquid
photoresist are caused by interference effects as the film
thickness changes owing to solvent loss. A compressional wave
is launched into the photoresist solution and partially reflected
back into the surface from the photoresist/air boundary. This
causes constructive and destructive interference effects to be
observed as the boundary distance changed. The visual
observation of the photoresist being dry coincides with the
end of the wild oscillations. Other effects persist in the sample
after the gross drying has occurred. Attenuation of the wave
slowly increases until the trend reverses itself at about 1200

s. The activity observed in the film levels off after about 5000
s has elapsed. Further research will be necessary before the
nature of the observed behavior can be completely understood.
The presence of this unexposed photoresist on the surface of
the SAW device provided a convenient opportunity to study
the effects of photo cross-linking of the resist. When polymers
are cross-linked the effect is to raise the Tg(Le., make the
polymer more brittle). This is seen in Figure 13. After il-
lumination with UV light, the attenuation of the wave is
reduced which is precisely the response expected. The sig-
nal-to-noise ratio obtained was poor. I t should be noted that
there was no attempt made to filter the signal either by analog
or digital means in both experiments. The important fact is
that it was possible to observe the effect of UV induced
cross-linking in a very small photoresist film. Improvements
in instrumentation could provide significantly greater sig-
nal-to-noise ratios.
ACKNOWLEDGMENT
The authors thank A. J. Wnuk and T. C. Ward for the
Detection of Explos ves with a Coated Piezoelectr c Quartz
Crystal
Yutaka Tomita, Mat H. Ho, and George G. Guilbault"
Department of Chemistry, University of New Orleans, New Orleans, Louisiana 70 722
A coated pierolelectric quartz crystal, which has potential use
as a simple device for assay of explosives, is used for the
detection of mononitrotoluenes (MNT). The detector can
indicate the presence of trinitrotoluene, the less volatile parent
molecule. Carbowax 1000 was found to be useful as a coating
for the Sensitive and selective detection. With the coating,
MNT vapor in the ppb-ppm range can be detected without
serious interferences. The response time observed was only
10 s and a complete reversibility of response was obtained
in less than 50 s. Some parameters that affect the efficiency
of the detector (amount of coating, interferences, flow rate,
temperature) were also investigated.
A highly sensitive and selective method for detection of
explosives is in great need. For example, airport surveillance
is only able to check for the presence of metallic materials but
cannot detect explosives strapped to an individual's body.
Some of the recent skyjackings have been caused by this
threat. A number of techniques for detection of explosives
have been reported using gas chromatography ( I , Z ) , mass
spectrometry (3),NMR ( 4 ) ,plasma chromatography ( 5 , 61,
thin-layer chromatography (71, and visible spectrometry (8).
While some of these laboratory techniques are capable of ppb
detection and may be satisfactory for a specific purpose, the
detection systems need elaborate techniques for operation and
are usually not portable and simple, thus are not useful for
field use.
In recent years there has been a growing interest in coated
piezoelectric quartz crystals, not only as a highly sensitive and
selective detector of various air pollutants (9) but also as a
simple, inexpensive, and portable device which is even small
enough to be carried in a worker's pocket (10). King ( I I ) ,
0003-2700/79/0351-1475$01.00/0
ANALYTICAL CHEMISTRY, VOL. 51, NO. 9, AUGUST 1979 1475
polymer film samples and valuable discussions.
LITERATURE CITED
Wohltjen, H., Dessy, R . E. Anal. Chem., preceding paper in this issue.
Ward, I.M. "Mechanical hoperties of Soli Polymers", Wiley Interscience:
New York, 1971; p 98.
Rosen, S.L. "Fundamental hinciples of Polymeric Materialsfor Practicing
Engineers"; Barnes & Noble, New York, 1971; p 229.
Wendlandt, W. W. "Thermal Methods of Analysis", 2nd ed., Wiley In-
terscience: New York, 1974.
Haldon, R . A,; Schell, W. J.; Simha, R. "Transitions in Glasses at Low
Temperatures," "Cryogenic Propertiesof Polymers", Koenig and Serafini,
Ed., Marcel Dekker: New York, 1968; p 152.
Haldon. R . A.; Schell, W. J.; Simha, R. Ref. 5 , p 148.
Dill, F. H.; Shaw, J. M. "Thermal Effects on the Photoresist AZ1350J,"
IBM J . Res. Dev. 1977, 21, 210.
Hatzakis, M., Thomas J. Watson Research Laboratories, P.O. Box 218,
Yorktown Heights, N.Y. 10598, private communication, April 25, 1978.
RECEIVED for review January 22,1979. Accepted May 1,1979.
The authors thank the Gillette Charitable and Educational
Foundation whose funds helped support this research. All
plots were made on a Benson Lehner Plotter, a gift from
Corning.
developed a sensitive piezoelectric-sorption detector for
monitoring hydrocarbons in the atmosphere. Janghorbani and
Freund (12) have described the use of these crystals as digital
sensors for sulfur compounds commonly found in pulp mill
effluents. Frechette and Fasching (13)have proposed their
use in a static system for the detection of sulfur dioxide.
Cheney et al. (14) have described several coatings suitable for
sulfur dioxide detection. Guilbault et al. (15-21) developed
a sensitive crystal cell design and coatings for organo-
phosphorus pesticides, and inorganic gases such as SO2,NO2,
NH3, HCl, and H2S in the atmosphere.
The principle of the detector is that the frequency of vi-
bration of an oscillating crystal is decreased by the adsorption
of a foreign material on its surface. A gaseous pollutant is
selectively adsorbed by a coating on the crystal surface,
thereby increasing the weight on the crystal and decreasing
the frequency of vibration. The decrease in the frequency in
proportional to the increase in weight due to the presence of
gas adsorbed on the coating, according to the following
equation (20).
AF = K-LC (1)
where AF is the frequency change (Hz), K is a constant which
refers to the basic frequency of the quartz plate, area coated,
and a factor to convert the weight of injected gas (9) into
concentration (ppm), and I C is concentration (ppm), of
sample gas. Previous works (22, 23) have shown that the
theoretical limit of detection for a coated crystal is about
g and that a commercially available 9-MHz crystal would have
a mass sensitivity of about 400 Hz/pg.
We examined many commercially available materials as
coatings for the detection of mononitrotoluene (MNT), which
is a volatile substance that can serve as a reliable indicator
for the presence of its less volatile parent, trinitrotoluene
C 1979 American Chemical Society