Sensors and Actuators B 107 (2005) 140–147

An high sensitivity optical sensor for chloroform vapours detection based

on nanometric film of δ-form syndiotactic polystyrene
M. Giordanoa,∗ , M. Russoa , A. Cusanob , G. Mensitieric
a Institute for Composite and Biomedical Materials, National Research Council, Smart Structures Laboratory, P.le Tecchio 80, 80125 Napoli, Italy
b Engineering Department, Optoelectronic Division, University of Sannio, Corso Garibaldi 107, 82100 Benevento, Italy
c Materials and Production Engineering Department, University of Naples, P.le Tecchio, 80125 Naples, Italy

Received 23 April 2004; received in revised form 31 July 2004; accepted 9 September 2004

Abstract

A film of syndiotactic polystyrene (sPS) in the nanoporous crystalline δ form has been used for the detection of chloroform in the vapor
phase at very low concentration The variation of the refractive index due to the chloroform sorption within the polymer has been used as
transduction property. Reflectivity measurements by a fiber optic refractometer, coated with a nanometric (73 nm) film has been performed at
very low pressure of chloroform (between 0.2 and 5 Torr) at three different temperatures (35, 49 and 56 ◦ C). Mass sorption experiments have
been concurrently performed with an electronic microbalance operating in the same conditions of the optical sensor. Major result from the
gravimetric tests is that the analyte is mainly adsorbed into the nanoporous phase where the penetrant molecules can be hosted with a certain
selectivity based on both size exclusion and host guest interactions. The quantitative correlation between the mass of analyte sorbed within
the polymer layer and the refractive index variation has been observed to be temperature independent. A phenomenological equation based
on the Lorentz–Lorenz law has been proposed to describe the effect of the chloroform uptake including both concentration and polarizability
changes on the refractive index of the sensible layer.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Optoelectronic sensor; Syndiotactic polystyrene; Clathtrate; Fiber optic

1. Introduction The heart of the chemical sensor is the sensitive element

Chemical detection represent one of the largest area of
study in sensoric and the development micro dimensioned
sensors with high selectivity is a fascinating challenge for
scientists. Chemical sensor can be schematically described
as composed of a sensitive part which, interacting with the
surrounding environment, collects and concentrate molecules
at or within the surface undergoing physical changes, and of
an opportune transducer that converts into an interpretable
and quantifiable term such modification of the sensing part.
The suitable combination of the sensing materials and sensing
systems is the key point for a successful sensor design.
∗ Corresponding author. Tel.: +39 081 7682603; fax: +39 081 2524932.
E-mail address: gmichele@unina.it (M. Giordano).
which is the interface between the transducer and external
environment so that the nature, the selectivity and sensitivity
of a chemical sensor depends upon these interactive materials
Good materials to use as sensing part should optimize
specific interactions with target analyte or narrow class of
analytes, should provide a fast and reversible diffusion of
the penetrants, small recovery times and should maintain the
physical state so as the geometry over several cycles of use,
in order to avoid hysteresis effects, and thus to ensure the
reproducibility [1].
In the field of the detection of volatile organic compounds
(VOC’s) a wide selection of materials seems to satisfy this re-
quirements. Artificial macrocyclic porphyrine [2] cryptands
and crown ethers singularly or coupled with other materi-
als like carbon (in the form of carbon black or fullerene) [3]
show a very high complexing ability with non polar organic

0925-4005/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2004.09.038
 M. Giordano et al. / Sensors and Actuators B 107 (2005) 140–147
compounds, but also a broad range of selectivity. Calixarenes
[4], instead, exhibit a good selectivity and a good complexing
ability, as they have a an intermolecular cavity chemically sta-
ble and of tunable size and a coordination selectivity. Specific
host–guest interactions can, then, be enhanced by opportune
designing of the molecule.
However, beside low molecular weight materials also
many polymers comply to many of the requirements listed
above, resulting to be suitable materials to employ in sen-
soric. Furthermore they can be deposited on several substrates
with easy processing techniques, and are low cost. In general
amorphous materials are used (in the form of elastomers or
glasses) as the crystalline phase [5,6], being too compact, is
usually impervious to penetrant.
Nevertheless an interesting exception is represented by the
syndiotactic Polystyrene (sPS) in the semicrystalline δ form
which is able to absorb also in the crystalline domains. This
polymer is, in fact, characterized by a nanoporous crystalline
phase with a regularly spaced array of nanocavities of well
defined size and shape, where penetrant molecules can be
hosted with a certain selectivity based on both size exclu-
sion and host guest interactions, and exhibits high sorption
capacity and an improved selectivity towards low molecular
weight organic substances, mainly chlorinated and aromatic
[13–15].
The natural step following the selective recognition of an
analyte, from the sensitive layer, is the signal transduction and
thus the choice of the opportune technique to read the physi-
cal changes occurring at the sensing part. In last years several
sensor technologies have been developed for the chemical va-
por detection, where usually the transducer converts a vapor
induced change in the physical property of the sensing layer
into an optical or electronic signal. Widely used are the mass
sensors like those usually referred as piezoelectric sensors,
(SAW, BAW, QCM), which act also like balances by measur-
ing the shift in the resonance frequency of the piezo crystal
due to the sorption of analyte within the sensing element,
that is directly related to the sorbed mass. Another interest-
ing class of sensor of large application is represented by the
impedance type sensors which are based on the changes in
resistivity or permittivity of conducting or insulating sensing
layers, deposited between contact lines, upon sorption of a
sample analyte.
Beside these, the fiber optic sensors represent another class
of sensors of recent fast growing interest. Several advan-
tages are in fact associated to fiber optic like the absence
of electrical interference that allows the remote real-time
sensing, the possibility to use them in harsh environments
as they are not subjected to corrosion and the possibility
to serve both as sensing data transportation system and as
transducer.
In a earlier work, Authors [7] reported the successful per-
formance of an optoelectronic sensing system for the measure
of refractive index, based on the sorption properties of a film
of δ form syndiotactic polystyrene, for the detection of traces
of chloroform and toluene down to 5 ppm (ml/ml) in a aque-
141
ous environment. The aim of the present work was not only to
investigate the suitability of the sensor for the detection of the
analyte in the vapor phase, but also to have quantitative infor-
mation about the correlation between the chloroform uptake
within the polymer sensible layer and the corresponding vari-
ation of the optical property. Measures of reflectance at very
small pressures of chloroform (down to 0.2 Torr) were, then,
carried out at three different temperatures (35, 49 and 56 ◦ C)
and the sorption isotherm curves obtained with the optoelec-
tronic sensor were properly compared with those obtained
from sorption tests by gravimetric analysis made with an elec-
tronic microbalance (CHAN 200) operating in the same con-
ditions of temperature and pressures. The correlation between
the sorbed mass and the variation of the polymer refractive in-
dex and the external pressure of chloroform was obtained and
interpreted on the basis of the Lorentz–Lorenz law. A full de-
scription of the analysis and of the results is presented along
discussion.
2. Materials and methods
2.1. δ Form SPS layer as vapor sensitive element
Syndiotactic polystyrene is a polymorph semi-crystalline
polymer exhibiting four different crystalline forms: α and
β characterized by a transplanar conformation of the chains
and two others δ and γ consisting of s(2/1)2 TTGG heli-
cal chains [8]. Among these crystalline structures the δ form
raises particular interest, as it is nanoporous [9]. It can be
obtained when the polymer is cast from solution, in fact, sPS
can clathrate the used solvent molecules housing them be-
tween helical chains. Over extraction of the host molecules
by suitable solvent treatment a metastabile nanoporous struc-
ture is obtained [10–12] (see Fig. 1). In this form sPS can
adsorb reversibly certain analytes, whose size and shape well
fit the nanocavities establishing specific host guest interac-
tions, when exposed to vapor or liquid environment where
these compounds are present even in traces. The nanoporous
structure of the δ sPS is responsible of its higher sorption
capability in respect with other semi-crystalline polymers as
it allows the penetration not only in the amorphous phase but
also within the crystalline domains that usually are more com-
pact and then impervious to penetrants. However a previous
study [13,14] showed that, for low concentration of analyte,
δ form sPS exhibits sorption levels in the amorphous phase
much lower than that of the crystalline phase; thus, when ex-
posed to very low concentration of analyte it can be safely
assumed that the sorption occurs almost completely in the
sole crystalline phase where only those molecules of proper
dimensions and which are able to establish host guest inter-
action with the nanocavities, like low molecular chlorinated
or aromatic compounds, are admitted to pass. This allows δ
sPS to be successfully used as polymeric coating for chemi-
cal sensing as well as for application in chemical separation
and water purification in membrane feature [15].
142 M. Giordano et al. / Sensors and Actuators B 107 (2005) 140–147

Fig. 1. Chain conformation in the sPS δ crystalline form. When the sensing film is cast from chloroform solution, ac planes corresponding to rows of parallel
helices with minimum interchain distances, are parallel to the film plan (uniplanar configuration). The grey shaded form represent the hosting cavity.

2.2. Materials and preparation the fiber optic sensor

probe

The sPS used for this work was supplied by Dow Chemical
Co. (Questra 101) presents a tacticity up to 98%, average
molecular weight (GPC) Mw = 320,000, polydispersity index
Mw/Mn = 3.9. The atactic PS was purchased by Aldrich with
an average molecular weight of 230,000 g/mol (GPC) and
specific density 1.04.
The fiber optic sensor probe was prepared by dip-coating
a sPS film from a chloroform solution of the polymer (1.5%
b.w.) onto the tip of a standard silica optical fiber 125 ␮m
diameter and of 9 ␮m core, which was previously perfectly
polished from the acrylic protection and cleaved with a preci-
sion cleaver in order to obtain a smooth and plane surface. The
clathrate thus formed was finally exposed to acetone vapors in
order to extract the solvent and obtain the empty nanoporous
δ form semi-crystalline sPS. The crystalline fraction of the
δ form obtained by a casting from a chloroform solution is
about the 50% by volume [12] and presents a strongly uni-
planar orientation, in other words the ac planes are parallel to
the sensor surface [16]. A schematic view of the basic sensor
design is reported in Fig. 2.
Reflectance measurements have been performed by light-
ing the sensing fiber with a broadband light source. To this
aim a superluminescent diode (40 nm bandwidth) centered at
1310 nm was used. A 2 × 2 in fiber coupler provides the nec-
essary connections between light source, sensing interface
and two receiving channel: one for reflected signal detection
and the other one for power monitoring in order to obtain well
compensated intensity measurements. More detailed descrip-
tion of the system set up can be found elsewhere [7]. Fig. 2. Scheme of the probe of the film refractometer and SEM image of the
The sensor head was, then, inserted in to a water-jacketed fiber coated tip.
stainless steel vacuum-tight cell by a special feed through
 M. Giordano et al. / Sensors and Actuators B 107 (2005) 140–147 143

[17]. The pressure of the analyte vapor into the test cell is mea-
sured by a pressure transducer with a resolution of 0.01 Torr
while a turbomolecular pump allows the evacuation of the
test cell down to 10−3 Torr. Refractometric measurements
consisted in recording the sensor output as the sorption of the
analyte in the nanocavities promotes a change of the polymer
layer refractive index.

2.3. Equation of the film refractometer

The optoelectronic sensor output I, consists in the ratio

between the reflected signal and the one corresponding to the
power monitoring [7] and it is proportional to reflectance R
at the polymer-fiber interface. The reflectance [18], in turn,
depends on the refractive index of the optical fiber, nf , of the
polymer film, n and of the external medium next, so as on the
film thickness d and the wavelength of the probe light λ, as
reported in the Eq. (1):

(r12 + r23 )2 − 4r12 r23 sin2 (δ)

I = αR = α (1)
(1 + r12 r23 )2 − 4r12 r23 sin2 (δ)

nf − n n − next 2πnd
r12 = ; r23 = ; δ= ;
nf + n n + next λ

where r12 , r23 are the reflectivity coefficients at the fiber-

polymer and polymer-vapor phase interfaces, respectively,
while δ is the phase shift that the λ wavelength light undergoes
when it passes through the polymer layer of thickness d and
α an optical coupling factor depending on the optical setup.
In spite of the apparent complexity, in the hypothesis that
upon sorption of the analyte the thickness of the sensing poly-
mer film undergoes only negligible changes, the refractome-
ter equation (Eq. (1)) relating the sensor output to the refrac-
tive index of the polymer can be linearized as follows: Fig. 3. (a) Linear approximation of the refractometer equation (Eq. (1), in the
case of negligible variation of the thickness of the film and (b) the diagram
reports both the response time and sensitivity as a function of film thickness
n = Kn I (2) as referred to a generic sensor with a 50 nm thick film.

where the constant Kn contains the optical coupling factor
α and the actual thickness d of the film [18]. Fig. 3a shows
the reflectance R as function of the refractive index of the
polymer film for different film thickness (refractive indexes
of the fiber nf as been set to 1.46 and of the external medium
next unity, respectively).
Few useful considerations can be made on the expected
performance of the optical sensor. In particular, the sensor
sensitivity ∂I/∂n and the response time θ ∝ d2 /D are both in-
creasing function of the film thickness. Fig. 3b shows the sen-
sor sensitivity, as theoretically evaluated from Eq. (1), and the
response time, both normalized to the value they attained for
a 50 nm thick layer. Obviously, the proper compromise be-
tween high sensitivity and fast response of the sensor involves
primarily the choice of the polymer thickness.
2.4. Gravimetric analysis
For gravimetric analysis, powder particles of 10 nm aver-
age diameter were used. The sPS samples were prepared by
milling films of the polymer, cast from chloroform solution,
exposed to CS2 vapors, boiled in acetone and then vacuum
dried at 60 ◦ C. The aPS, powders were obtained milling poly-
mer pellets without any previous treatment.
The apparatus for the gravimetric analysis consists in a
controlled atmosphere (chloroform vapor pressure at a con-
trolled temperature) electronic microbalance, CAHN D200,
with a sensitivity equal to 0.1 ␮g. The chloroform pressure
was measured using a MKS Baratron pressure transducer
with a full scale reading of 10 Torr, a sensitivity of 10−3 Torr
and an accuracy of 0.15% of the readout. The full detailed
144 M. Giordano et al. / Sensors and Actuators B 107 (2005) 140–147
description of the device is reported in a previous work [19].
The equipment was used to determine the mass gain of the
powder samples due to sorption when exposed to chloroform
vapors. Gravimetric measurements were carried out on pow-
der samples of δ form sPS and aPS at the same temperatures
and in the same range of chloroform pressures of the refrac-
tometric analysis.
3. Results
3.1. Gravimetric sorption measurements
The “integral sorption” tests were performed by expos-
ing powder samples to sudden step increases of pressure
of chloroform from zero to the desired value and for each
sorption test a different specimen was used. Sorption tests
were carried on both the semycrystalline polymer, δ form
sPS, and on the atactic polymer aPS at 35, 49 and 56 ◦ C, in
the range 0–10 Torr. Measurements on an atactic polystyrene
were made in order to simulate the sorption into the amor-
phous phase of the semi-crystalline polymer and thus to es-
timate the characteristic sorption of the δ nanoporous crys-
talline phase. Fig. 4 reports the sorption isotherms for chlo-
roform obtained by gravimetric measurements on δ form sPS
together with the atactic PS at the three temperature, 35, 49
and 56 ◦ C. The sorption isotherms are reported as grams of
chloroform sorbed per 100 g of polymer (corresponding to
the equilibrium sorption amounts) versus chloroform vapor
activity, a (expressed as the ratio between the pressure of
chloroform, p, and its vapor pressure, p0 , assuming an ideal
behavior of the vapor phase), i.e. the relative pressure of chlo-
roform.
Equilibrium properties of the semi-crystalline polymer is
a properly weighted combination of the contribution of the
amorphous and crystalline phase. In the hypothesis that the
Fig. 4. Sorption isotherms of chloroform at different temperatures for sPS
and aPS (continuous lines are only guides for the eyes).
amorphous phase in the semicrystalline polymer is equivalent
to that of atactic polystyrene, from the curves in Fig. 4, it can
be inferred that the sorption amount in the amorphous phase
of δ sPS is negligible with respect to that in the crystalline
phase.
3.2. Fiber optic refractometer experiments
3.2.1. Measurements of the refractive index of sPS
Dependence of the reflectance upon the light source wave-
length was used to estimate the refractive index of the syn-
diotactic polystyrene. To this aim, broadband measurements
of the power reflected at the cleaved fiber interface Ib(λ) and,
after the deposition of the sensing film, at the fiber-polymer
interface, If(λ), in air, were performed using an Optical Spec-
trum Analyzer (OSA). The fiber optic has been not discon-
nected from the optical circuit to the spectrum analyzer during
the film deposition and the interrogation broadband signal has
continuously monitored to evaluate the launching conditions.
By taking the ratio between the two spectra, a function
is obtained, If/Ib = f(λ; n, d), where the only unknown pa-
rameters are the refractive index n and the thickness d of the
polymer film. The optical coupling factor is, in fact, elided in
the ratio, the fiber optic refractive index is known and equal to
1.46278@1310 nm [20] and the external medium refractive
index (air at room temperature) is assumed unitary.
As an example, Fig. 5 shows the ratios If/Ib(λ; n, d) mea-
sured for five films @ 25 ◦ C together with the non linear
fit of Eq. (1) to the experimental data. The evaluations of
the refractive index at different temperatures obtained with
the method described and the thermo-optic coefficient are
reported in Table 1.
The value obtained via refractometric measurements were
consistent to those by Rizzo et al. [21] found at room temper-
ature with an Abbe refractometer (n = 1.596). However their
measurements were made upon a film of higher thickness
120 ␮m.
Fig. 5. Ratios of the spectra of sPS films and nude fiber at 25 ◦ C (continuous
lines are the best fit).
 M. Giordano et al. / Sensors and Actuators B 107 (2005) 140–147 145

Table 1
Refractive index of sPS at different temperatures and thermo optic coefficient
◦
T ( C) 25 35 49 56 dn/dT, K−1
n 1.5781 1.5741 1.5684 1.5656 4.03 × 10−4

3.2.2. Refractometric sorption tests

Analogous measurements to those made by gravimetry
were carried out using the optical sensor. A δ form sPS film
of 73 nm thickness was used to perform sorption tests at three
different temperatures: 35, 49 and 56 ◦ C. The estimation of
the refractive indexes made previously enables the evaluation
of the refractometer calibration constant Kn resulted to be
equal to 0.493.
Measurements of reflectivity were carried out for different
pressures of chloroform, in a range where it can be safely as-
sumed that the sorption occurs preferentially in the crystalline
phase [22] (from 0.2 Torr to about 4.5 Torr). Each injection of
analyte was made under vacuum (10−3 Torr) and at the end Fig. 7. Sorption isotherms of chloroform at different temperatures as
of the test, to verify the reversibility of the sensor, the test recorded by the optical sensor (continuous lines are only guides for the
chamber was completely evacuated from the vapours. eyes).
The typical step responses of the fiber optic sensor upon
analysis. However, the gravimetric isotherms define the ther-
sorption of an analyte are shown in Fig. 6, in particular the
modynamic of the phase equilibrium for chloroform between
diagram reports the response to an instantaneous increase of
the vapor phase and the polymer film, while the constitutive
the chloroform pressure from 0 to 0.21 Torr (a = 3.3 × 10−4 )
relationship between the refractive index and the chloroform
and to 4.33 Torr (a = 6.8 × 10−3 ) at 56 ◦ C.
sorption has to be determined taking in to account the vari-
The standard deviation of the signal in equilibrium con-
ations of both density and polarizability due to the presence
ditions (vacuum and at the equilibrium sorption) was eval-
of the chloroform molecules hosted in the polymer layer.
uated to be σ I = 9.9 × 10−5 ± 0.7 × 10−5 while the resolu-
tion of the used optical sensor, evaluated as σ n = Kn σ I was
σ n = 4.9 × 10−5 . The reflectivities at equilibrium at each tem-
4. Discussion
perature were then reported as function of the chloroform ac-
tivity a = (p/p0 ) and the isotherm curves obtained are shown
4.1. Correlation between the optical output and the
in Fig. 7.
amount of adsorbed chloroform
Sorption isotherms as recorded by the optical sensor
shown a behavior similar to those obtained by the gravimetric
The refractive index of the polymer film changes as a con-
sequence of the chloroform sorption into the sPS sensitive
layer. Fig. 8 shows the change of the refraction index n due
to the adsorbed chloroform concentration C within the poly-
mer, such curve has been obtained by the double interpolation
of experimental data at different temperatures relative to the
gravimetric (Fig. 4) and refractometric (Fig. 7) tests. The
curves slightly depends on the temperature: a given amount
of chloroform adsorbed in the polymer induces the same vari-
ation in the refractive index whatever is the temperature.
However, the correlation between the refractive index
changes and the chloroform concentration within the sen-
sitive film was made on the basis of the Lorenz–Lorentz law:
n2 − 1 N
= ρβ (3)
n +2
2 3Mε
where ρ is the density, β the polarizability, N the Avogadro
number, M molecular weight of the repetitive polymer unit
and ε the vacuum permittivity. In the present case the re-
fractive index is affected by the combined variation of the
Fig. 6. Sensor responses at different analyte concentrations at 56 ◦ C. density and the polarizability. In fact, beside the linear in-
146 M. Giordano et al. / Sensors and Actuators B 107 (2005) 140–147

Fig. 9. Sorption dynamic as recorded by the fiber refractometer in terms of

chloroform concentration (dash line is the best fit to Eq. (6)).

Fig. 8. Change of refraction index due to the chloroform adsorption in sPS

at different temperatures (dash line is the best fit to Eq. (4)). layer. So, as an example, the step response to an injection of
vapour pressure of 4.33 Torr at 56 ◦ C as recorded by the fiber
crease of density as consequence of sorption, there is also an
optic film refractometer (see Fig. 6) can be converted (Fig. 9)
effect on the average polarizability (Eq. (3)) due to specific
to the corresponding chloroform concentration by using the
interactions between the chloroform molecules and the cav-
correlation of Eq. (4). Fig. 9 shows the best fit of Eq. (5)
ities walls, that is not trivial to retrieve. To take in to account
to data obtained with a diffusivity of D = 33.3 × 10−13 cm2 /s
such concurrent phenomena an empirical equation derived
which is rather higher than the value measured by gravimetric
from Eq. (3) was introduced:
analysis, D = 8.6 × 10−13 cm2 /s. This is likely related to the
n2 − 1 different morphology of the films used to perform the gravi-
+ 0.5 = ACγ (4) metric sorption experiments as compared with the rather thin-
n2 + 2
ner layer deposited on the fiber tip. In fact, differences in the
where the factor 0.5 provide the equation consistence for
crystallinity levels and in the orientation of the crystalline do-
C = 0 and γ is a power law index accounting for the effect
mains are possible and this can affect the apparent diffusivity
of density increase and unknown polarizability change due
in view of differences in diffusional profiles of the amorphous
to chloroform adsorption.
and of the crystalline phase and of the anisotropy [24] of the
Fig. 8 shows the refractive index changes as a function
mass transport properties of the crystalline domains.
of the concentration of chloroform sorbed as results from the
best fit of the three isothermal set of data with Eq. (4) while the
A and γ parameters estimated resulted to be A = 1.15 × 10−5
and γ = 1.36. 5. Conclusions

4.2. Kinetic of diffusion process The performance of an optoelectronic sensing system

based on the sorption properties of a film of δ form syn-
The concentration C of the penetrant at the fiber optic- diotactic polystyrene, previously used [7] for the detection
polymer interface, in the case of unidimensional mass trans- of VOC’s in aqueous environments, was here successfully
port in a polymer layer, at initial concentration C0 , of thick- tested for the detection of traces of chloroform (down to 10−4
ness d with an interface instantaneously exposed to the ex- chemical activity) in the vapor phase. As discussed in Sec-
ternal solution at Cd concentration and the other interface tion 2.2, the sensor performance in terms of sensitivity and
impervious to the mass flux (as is in the case of the thin film response time inversely depends on the sensible layer thick-
cast upon the fiber distal end), is described by: [23]: ness. In the present case, a sPS film of 73 nm was chosen
  that demonstrated a minimum signal to noise ratio  = I/σ I
∞
C − C0 4
(−1)n −D(2n + 1)2 π2 t of the order 100 (at 56 ◦ C and 0.2 Torr) and a maximum re-
=1− exp (5) sponse time of about 16 s (at 56 ◦ C and 0.2 Torr). In addi-
Cd − C 0 π 2n + 1 4d 2
n=0 tion, gravimetric sorption experiments demonstrated that, in
The correlation described in Eq. (4) allows to convert the the range of investigated chemical activities, the chloroform
refractometric responses to variation of the external pressure is mainly adsorbed into the nanoporous δ crystalline phase
of analyte in terms of concentration of analyte in the polymer of the polymer being 50% of the whole material volume.
 M. Giordano et al. / Sensors and Actuators B 107 (2005) 140–147
Such finding, based on the evidence that a class of penetrant
molecules can be hosted within the crystal cavities only due
to both size exclusion and host guest interactions, guaranties a
certain selectivity towards the chloroform (even if a quantita-
tive evaluation of the polymer selectivity shall involve further
work).
Sensor calibration enabled to retrieve the effective changes
of refractive index due to the analyte sorption within the
polymer layer and permitted a quantitative correlation be-
tween the concentration of sorbed chloroform, the variation
of the polymer refractive index and the external pressure of
chloroform. As matter of fact, the sorption of chloroform
induces stronger changes in refractive index, approximately
∂n/∂C ≈ 2 × 10−3 , if compared with the thermo-optic coef-
ficient of sPS, ∂n/∂T = 4 × 10−4 K−1 ; as a consequence the
dependence of refractive index on the concentration of sorbed
chloroform results non linear and poorly dependent on tem-
perature. In addition, an empirical equation has been pro-
posed on the basis of the Lorentz–Lorenz law accounting for
density and polarizability dependence of refractive index on
the mass of chloroform adsorbed.
In conclusion, the proposed sensor system, together with
the derived correlation between the concentration of sorbed
chloroform and the variation of the polymer refractive index
permits the quantitative monitoring of the vapor chloroform
composition at very low chemical activities levels.
References
[1] J.W. Grate, M.H. Abraham, Solubility interaction and design of
chemically selective sorbent coatings for chemical sensor and ar-
rays, Sens. Actuators, B 3 (1991) 85–111.
[2] C. Di Natale, D. Salimbeni, R. Paolesse, A. Macagnano, A.
D’Amico, Porphyrins-based opto-electronic nose for volatile com-
pounds detection, Sens. Actuators, B 65 (2000) 220–226.
[3] H.B. Lin, J.S. Shih, Fullerene C60-cryptand coated surface acoustic
wave quartz crystal sensor for organic vapors, Sens. Actuators 92
(2003) 243–254.
[4] S.K. Matè, G. Nagy, L. Collar, Investigation of the interaction of
calixarenes (host) and neutral benzotrifluoride (guest) conmparisn
of luminescence characteristic of calixarenes with results of model
calculation relating to complex formation, Sens. Actuators, B 76
(2001) 545–550.
[5] A.S. Michaels, H.J. Bixler, Flow of gases through polyethylene [and
rubbery polymers], J. Polym. Sci. 50 (1961) 413–439.
[6] C.E. Rodgers, Permeation of gas and vapors in polymers, in: J.
Comyn (Ed.), Polymer Permeability, Elsevier, New York, 1985, Ch.
2.
[7] M. Giordano, M. Russo, A. Cusano, G. Mensitieri, G. Guerra, Syn-
diotactic polystyrene thin film as sensitive layer for an optoelectronic
chemical sensing device, Sens. Actuators B (in press).
147
[8] G. Guerra, V.M. Vitagliano, C. De Rosa, V. Petraccone, P. Corradini,
Polymorphism in melt crystallized syndiotactic polystyrene samples,
Macromolecules 23 (5) (1990) 1539–1544.
[9] V. Petraccone, F. Auriemma, F. Dal Poggetto, C. De Rosa, G.
Guerra, P. Corradini, On the structure of the mesomorphic form of
syndiotactic polystyrene, Makromolekulare Chemie 194 (5) (1993)
1335–1345.
[10] C. Manfredi, C. De Rosa, G. Guerra, M. Rapacciuolo, F. Auriemma,
P. Corradini, Structural changes induced by thermal treatments on
emptied and filled clathrates of syndiotactic polystyrene, Macromol.
Chem. Phys. 196 (9) (1995) 2795–2808.
[11] G. Milano, V. Venditto, G. Guerra, L. Cavallo, P. Ciambelli, D.
Sannino, Shape and volume of cavities in thermoplastic molecular
sieves based on syndiotactic polystyrene, Chem. Mater. 13 (2001)
506–1511.
[12] C. De Rosa, G. Guerra, V. Petraccone, B. Pirozzi, Crystal struc-
ture of emptied clathrate form (␦e form) of syndiotactic polystyrene,
Macromolecules 30 (1997) 4147–4152.
[13] G. Guerra, C. Manfredi, P. Musto, S. Tavone, Guest conformation
and diffusion into amorphous and emptied clathrate phases of syn-
diotactic polystyrene, Macromolecules 31 (4) (1998) 1329–1334.
[14] G. Mensitieri, V. Venditto, G. Guerra, Polymeric sensing films ab-
sorbing organic guests into a nanoporous host crystalline phase, Sens.
Actuators, B: Chem. B92 (3) (2003) 255–261.
[15] G. Guerra, G. Mensitieri, V. Venditto, Method for the detection of
organic pollutants using syndiotactic polystyrene polymers as sensing
elements, US Pat. Appl. Publ. (2002) 7.
[16] P. Rizzo, M. Lamberti, A.R. Albunia, O. Ruiz de Ballesteros, G.
Guerra, Cristalline orientation in syndiotactic polystyrene cast films,
Macromolecules 35 (2002) 5854–5860.
[17] E.R.I. Araham, E.A. Cornell, Teflon Feedthrough for coupling optical
fibers into ultrahigh vacuum systems, Appl. Opt. 370 (10) (1998)
1762–1763.
[18] A. Cusano, G.V. Persiano, M. Russo, M. Giordano, Novel optoelec-
tronic sensing system for thin polymer films glass transition inves-
tigation, IEEE Sens. J. (in press).
[19] C. Manfredi, A.M. Del Nobile, G. Mensitieri, G. Guerra, M. Rapac-
ciuolo, Vapor sorption in emptied clathrate samples of syndiotactic
polystyrene, J. Polym. Sci., Part B: Polym. Phys. 35 (1) (1997)
133–140.
[20] A. Cusano, A. Cutolo, M. Giordano, L. Nicolais, Optoelectronic
refractive index measurements: application to smart processing, IEEE
Sens. J. 3 (6) (2003) 781–787.
[21] P. Rizzo, A. Costabile, G. Guerra, Perpendicular orientation of host
polymer chains in clathrate thick films, Macromolecules 37 (8)
(2004) 3071–3076.
[22] P. Musto, G. Mensitieri, S. Cotugno, G. Guerra, V. Venditto, Prob-
ing by time-resolved FTIR spectroscopy mass transport, molec-
ular interactions, and conformational ordering in the system
chloroform–syndiotactic polystyrene, Macromolecules 35 (6) (2002)
2296–2304.
[23] J. Crank, The Mathematics of Diffusion, second ed., Clarendon
Press, Oxford, 1975.
[24] G. Milano, G. Gaetano, F. Mueller-Plathe, Anisotropic diffusion
of small penetrants in the δ crystalline phase of syndiotactic
polystyrene: a molecular dynamics simulation study, Chem. Mater.
14 (7) (2002) 2977–2982.