Combined Photothermal Lens and Photothermal Mirror
Characterization of Polymers
Odon S. Aréstegui,a Patricia Y.N. Poma,a Leandro S. Herculano,a
Gustavo V.B. Lukasievicz,a Francine B. Guimarães,a Luis C. Malacarne,a
Mauro L. Baesso,a Stephen E. Bialkowski,b Nelson G.C. Astratha,b,*
a
Departamento de Fı´sica, Universidade Estadual de Maringá, Maringá, PR 87020-900 Brazil
b
Department of Chemistry and Biochemistry, Utah State University, Logan, UT 84322 USA
We propose a combined thermal lens and thermal mirror method as
concurrent photothermal techniques for the physical characteriza-
tion of polymers. This combined method is used to investigate
polymers as a function of temperature from room temperature up to
170 8C. The method permits a direct determination of thermal
diffusivity and thermal conductivity. Additional measurements of
specific heat, linear thermal expansion, and temperature-dependent
optical path change are also performed. A complete set of thermal,
optical, and mechanical properties of polycarbonate and poly
(methyl methacrylate) samples are obtained. Methods presented
here can be useful for in situ characterization of semitransparent
materials, where fast and non-contacting measurements are
required.
Index Headings: Photothermal mirror; Photothermal lens; Photo-
thermal methods; Material characterization.
INTRODUCTION
Photothermal methods have been extensively used to
measure the thermal, optical, and mechanical properties
of a variety of solids, liquids, and gases for many
decades.1-5 The photothermal methods are based on
light-induced heat generation in the sample, followed by
changes in temperature or related thermodynamic
properties of the sample. The thermally induced pertur-
bations are detected by measuring, for instance, internal
changes in refractive index, surface deformation, and
pressure, comprising together a group of very sensitive
spectroscopic tools for material characterization.1–5
The light-induced changes in the refractive index of
the sample initially follow the spatial distribution of the
excitation laser beam, and a time-dependent optical
element is formed in the excited volume of the sample.
The spatial distribution has a radial profile and a thermal
lens (TL) effect.6,7 This effect can be probed using
another laser beam passing through the optical excited
volume. The TL affects the propagation of the probe
beam, and the signal is measured by analyzing the time-
dependent far-field probe beam focusing or defocusing.6
The TL method has been used as a highly sensitive
technique in optical absorption.8–16 Its strength is related
to the optical absorption coefficient, the temperature
dependence of the optical path change, and the analyte
concentration. The time evolution of the TL effect
Received 28 November 2013; accepted 7 February 2014.
* Author to whom correspondence should be sent. E-mail: astrathngc@
pq.cnpq.br.
DOI: 10.1366/13-07404
0003-7028/14/6807-0777/0
Volume 68, Number 7, 2014 Q 2014 Society for Applied Spectroscopy
depends on the heat diffusion properties of the sample.
Transient signal analysis gives direct quantitative
access to thermal and optical properties of the sam-
ple.7,12-15 In addition, the remote characteristics of the TL
method make this appropriate for measurements in a
controlled environment, where temperature changes or
other external fields are applied.14,17,18
Thermal lens measurements require the transmis-
sion of both the probe and the excitation beams through
the sample, thus limiting the applications to semitrans-
parent materials. An alternative detection based on
surface deformation can be used for material charac-
terization of semitransparent and opaque materi-
als. 1 9 – 2 9 Surface deformation occurs when an
excitation laser beam irradiates a solid sample,
resulting in expansion/contraction of the surface. A
reflected probe laser is used to detect the deformation
in the thermal mirror (TM) effect.30 The TM effect has
been exploited in several photothermal techniques that
are fast, non-contacting, and highly sensitive tools for
material characterization.1,20,24,29 The effect can be
measured as the TL is measured, by analyzing the
focusing/defocusing far-field probe beam reflected off
the sample surface.29,31,32 Its amplitude is directly
related to the optical absorption and thermal expansion
coefficients. Like the TL effect, the time evolution of the
deformation depends on the heat diffusion properties of
the sample. Thus, measuring the transient effect allows
direct quantitative access to thermal, optical, and
mechanical properties of the material.24–29 In addition,
recent theoretical developments opened the way for the
application of these methods for analytical character-
ization of transparent to opaque solids,1,6 considering
the effects of population lens in fluorescent materials
and photochemical reactions and mass diffusion during
laser excitation.33–36
The TM method can be used concurrently with the TL
method.37 The apparatus can be compact and fully
automated, making this especially interesting for in situ
measurements. In situ testing is indispensable for
preproduction control and quality monitoring. Measuring
and investigating materials at production conditions is,
in fact, pointed out as the single most challenging issue
among polymer and materials laboratories.38 This paper
uses a concurrent photothermal method for fast polymer
characterization. Since physical properties of polymers
may be strongly dependent on temperature, it is
desirable to measure their absolute values as a function
of temperature. Here, TL and TM methods are used
APPLIED SPECTROSCOPY 777
concurrently to investigate polymers as a function of
temperature, from room temperature up to 170 8C.
Thermal diffusivity and thermal conductivity are mea-
sured in addition to specific heat, linear thermal
expansion, and temperature dependence of optical path
change. A complete set of thermal, optical, and
mechanical properties of polycarbonate and poly (methyl
methacrylate) samples is obtained. It is shown that the
concurrent method presented here can be a useful tool
for in situ characterization of semitransparent materials
where fast and non-contacting measurements are
required.
THEORY
The basic principle of the photothermal techniques
employed in this work is the photoinduced heat
generation using nonradiative decay processes follow-
ing optical excitation of a sample. In this work, a single-
mode TEM00 laser beam is used to excite a solid sample,
and another single-mode TEM00 laser beam, nearly
collinear to the excitation beam, is used to probe the TL
and TM effects. Figure 1 shows a schematic diagram of
the laser beams at the sample. The probe beam travels
through the sample and probes the change in the
refractive index resulting in the TL effect. The reflected
probe beam fraction is affected by surface deformation
resulting in the TM effect. The radii of the excitation and
probe beams at the sample are w0e and w1p , respec-
tively. The probe beam propagates along the z direction
and the sample is located at z = 0. Photodetectors are
used to monitor the transmitted and reflected probe
beam intensity variations in the far-field. The distance
between the sample and the photodetector plane is Z2,
and the distance between the sample and the probe
beam waist of radius w0p is Z1.
The theoretical descriptions for the TL and TM effects
entails calculations of the sample temperature change
and the effects of this temperature change on the optical
path change (TL) and the thermoelastic surface defor-
mation.39,40 Thermal state perturbations produce phase
shifts in the probe beam wave front, altering the complex
amplitude of the probe beam at the detector plane. The
probe beam intensity changes past a pinhole spatial
filter. Only the central part of the probe beam is
monitored at the detector, leading to further simplifica-
tions in the modeling.6,29
Concerning the transparent polymers investigated in
this work, the low optical absorbing TL and TM models
FIG. 1. Geometrical representation of the laser beams for the TL and
TM experimental setups.
778 Volume 68, Number 7, 2014
could be used.6,31 The advantage of using the weak
absorbing approximation is that modeling becomes
relatively simple, and semianalytical expressions can
be used to describe the TL and TM transient signals. This
approximation has been extensively tested and used to
model previous experiments.6,7,12–17,29–31 The semiana-
lytical expressions have been shown to produce accu-
rate results for TL and TM effects in the semitransparent
materials studied to date. Also assumed is that the
dimensions of the sample are large compared with the
excitation beam radius, avoiding edge effects, and that
the optical absorption of the sample is low enough that
the excitation laser intensity is not attenuated along the
direction of travel. The laser induced temperature
change in the sample, DT(r,t), is given by the solution
of the heat diffusion equation.6
Sample deformation caused by the temperature
gradient described evolves following the Navier-Stokes
thermoelastic equation.38 The axially symmetric radial
nature of the Gaussian heat source requires the problem
to be treated in cylindrical coordinates, and, in the
quasistatic approximation, the solution for the surface
displacement uz (r,t) for a sample of thickness L has
been proposed by introducing displacement potential
functions.30,38 The strength of the TM effect is
Pe Ae aT ð1 þ mÞ/
hTM ¼  ð1Þ
kp k
where aT is the linear thermal expansion coefficient, m is
the Poisson ratio, kp is the probe beam wavelength, k is
the thermal conductivity, Pe = P0 (1  R), P0 is the
excitation power, R is the sample surface reflectivity, Ae
is the optical absorption coefficient at the excitation
beam wavelength ke, and / is the heat yield: the amount
of absorbed energy converted to heat.
In addition to the surface deformation, the sample’s
temperature rise distribution produces a refractive index
change. Both effects act as optical elements causing
phase shifts to the transmitted (TL) and reflected (TM)
probe beam. In two limiting cases, the plane stress and
the plane strain approximations, the phase shift for the
TL effects is directly proportional to the temperature
change, UTL = (2p/kp) L(ds/dT)TL [DT(r, t)  DT(0, t)], with
(ds/dT)TL describing the temperature coefficient of the
optical path change.39 For the TM effect, the phase shift
is related to the surface deformation by UTM = (2p/kp)
2[uz(r,t)  uz(0,t)], with uz(r,t).31 The produced phase
shifts are thus7,32
Z t   
1 2mg
UTL ðg; t Þ ¼ hTL 1  exp  d s ð2Þ
0 tc þ 2s 1 þ 2s=tc
and
Z
w20e ‘ coshðLaÞ  1
UTM ðg; t Þ ¼ hTM
tc 0 La þ sinhðLaÞ
Z t 
w20e ð1þ2s=tc Þa2 =8
3 e ds
0
 
pffiffiffiffiffiffiffi
3 J0 ðaw0e mg Þ  1 d a ð3Þ
Here, J0(x) represents the Bessel function of the first
kind, g ¼ ðr =w1p Þ2 , m ¼ ðw1p =w0e Þ2 , tc ¼ w20e =4D is the
characteristic thermal time constant, D = k/qCp is the
thermal diffusivity of the sample, and Cp and q are
specific heat and mass density of the sample, respec-
tively. The strength of the TL effect is given by
Pe Ae Lðds=dT ÞTL /
hTL ¼  ð4Þ
kP k

The transmitted and reflected probe beams propagate to

the detector plane in the far-field at a distance Z2 from
the sample. The propagation can be treated using
Fresnel diffraction theory. The time-dependent intensity
variation of the central portion of the probe beam at the
detector is dependent on the phase shift Uj (g,t)
produced by either the thermal lens (j  TL) or the
thR ‘e r m a l m i r r o r ( j  T M ) e f f e c t s a s I ( t ) =
j 0 exp½ð1 þ iV Þg  iUj ðg; t Þdgj2 :6,29
The geometrical parameter V = Z1/Zc þ Zc [(Z1/Zc)2 þ
1]/Z2, and Zc is the confocal distance of the probe beam.
I(t) is calculated by substituting one of the equations for
the phase shift, Eqs. 2 or 3, into I(t) and carrying out FIG. 2. Schematic of the TL and TM experimental setup. Mi, Li, and Pi
numerical integration over a, s, and g. Though it is stand for mirrors, lenses, and photodiodes, respectively. The experi-
convenient in most applications to simplify the TL signal mental parameters are w0e = 79 lm, w1P = 515 lm, m = 42.5, and V =
6.0.
by assuming that the phase shift induced is very small,
i.e., UTL(g, t)  1, and the approximation e iUðg;t Þ  1 
iUðg; t Þ holds, leading to the well-known analytical continuous-wave single-mode TEM00 He–Ne laser at
expression6 kp = 632.8 nm (Melles Griot, Model 25-LHR-151-249),
8 nearly collinear to the excitation beam (angle ,18), is
< hTL used to probe both the TL and the TM effects. After
Iðt Þ ¼ Ið0Þ 1  tan1 being reflected off of the sample surface, the probe
: 2 beam propagates to the photodetector P2 positioned in
2 3 a far-field (Z2 . 4 m) and probes the TM effect. Its
2

g
2mV
34 5 photodetector P3 and probes the TL effect. P2 and P3
tc ½ð1 þ 2mÞ2 þ V 2 =2t þ 1 þ 2m þ V 2
ð5Þ
The temperature changes induced in a sample are
generally small in the TL and in the TM experiments,
,1 8C, which, in turn, produce similarly small surface
refractive index changes. Consequently, changes in the
probe beam intensity due to surface reflectivity effects
can be safely neglected without affecting the accuracy.
EXPERIMENTAL SECTION
The TL and TM experiments can be concurrently
arranged in a way that both measurements can be
performed simultaneously. The schematic diagram of
the TL–TM apparatus used in this work is presented in
Fig. 2. The method is represented in the dual beam
mode-mismatched experimental configuration, in which
the sample is excited and probed using beams of
different diameters. The experiments are very similar in
essence to apparatuses previously described in many
reports.6–17,29,33 The excitation source is a continuous-
wave single-mode TEM00 Arþ ion laser at ke = 514.5 nm
(Coherent, Innova 90). A mechanical shutter (ThorLabs,
Model SH05) controls the exposure of the excitation
beam on the sample. The excitation beam was focused
in the sample using a 0.25 m focal length lens. A
transmission through the sample propagates to the
(ThorLabs, Model DET100A/M) were assembled with
pinholes and probe beam laser line filters. Only the
central part of the probe beam is then detected using
either photodiode and recorded using a digital oscillo-
scope (Tektronix, Model TDS1001B). The oscilloscope is
triggered by P1 (ThorLabs, Model PDA10A). The
response time of the photodiodes is ,50 ls. The
experimental parameters are shown in the caption of
Fig. 2, which were measured as described else-
where.6,14 A computer was used to control (using
Labview) the experimental apparatus and the measure-
ments.
A sample holder containing a heater and a heat sink
device was used for temperature data measurements.16
Thermal paste was used to improve the thermal contact
between the sample and the thermal reservoir. The
heater temperature was controlled using a temperature
controller (LakeShore, Model 340) with a resolution of
0.01 8C.
Polymers of different thicknesses were investigated in
this work. Polycarbonate (PC from Sigma-Aldrich Inc.)
and poly(methyl methacrylate) (PMMA from Diamond
Inc.) samples were prepared for the TL–TM measure-
ments in cylinders of radius of 10 mm and polished in
different thicknesses.
In addition to the photothermal measurements, a
homemade thermal relaxation calorimeter41 and a

APPLIED SPECTROSCOPY 779


FIG. 3. Normalized TL and TM signals, I(t)/I(0), for PC and a TL signal
for PMMA at room temperature.
commercial dilatometer (Netzsch, Model DIL402PC)
were used to measure the specific heat and the linear
thermal expansion coefficient, respectively, as a function
of temperature. The temperature dependence of the
optical path change was measured using an optical
interferometer,42 and mass density and refractive index
measurements were performed using a standard Archi-
medes method and an interferometer,43 respectively.
RESULTS AND DISCUSSION
The samples were first characterized at room
temperature. For the TL–TM experiments, the samples
were excited at different excitation power levels. More
than 100 transients were averaged at each excitation
power. Figure 3 shows examples of TL and TM
transients for PC (L = 1.00 mm) and a TL transient for
PMMA (L = 1.82 mm) samples. For the normalized TL
signal, Fig. 3a, the transients results from a decreasing
intensity at the photodetector. A decreasing signal is a
result of a defocusing thermal lens forming in the
sample. A divergent thermal lens results from (ds/dT)TL
, 0. Most polymers presented in this report exhibit a
divergent thermal lens. As for the normalized TM
signal, Fig. 3b, the decreasing signals arise from
surface expansion due to the positive linear thermal
expansion coefficient of the polymer samples. The
expansion produces a convex mirror, which in turn
defocuses the probe beam intensity at the pinhole-
detector plane. The transients were obtained with
excitation power levels of up to 150 mW, and a few
examples are displayed in Fig. 3b. TM measurements
were performed only on PC samples.
The signal decay times depend directly on the heat
diffusion properties of the samples, while the amplitude
780 Volume 68, Number 7, 2014
of both the TL and the TM effects depend on the optical
path change and thermal expansion of the sample,
respectively. The thermal diffusivity D and the parameter
hTL and hTM were obtained from regression using the
theoretical models, Eq. 5 for TL, and I(t) with Eq. 3 for TM.
Regression with the TM model was performed using the
‘‘NonlinearModelFit’’ function in Wolfram Mathematica 7.
Thermal diffusion constants are presented in Table I. The
thermal constants are found to be D = (1.8 6 0.1) 3 107
m2 s1 for PC and D = (0.8 6 0.1) 3 107 m2 s1 for
PMMA. These are within the range of values expected for
these materials.44 The signal amplitudes hTL and hTM
depend on the excitation power. Figures 3c and 3d shows
the excitation power dependence of these amplitudes.
From the linear fit, the coefficients hTL Pe1 L1 and hTM
Pe1 are obtained. Average values are presented in
Table I. hTL and hTM are directly related to the optical
absorption coefficient, heat yield parameter, thermal
conductivity, and optical path change for hTL, or the
linear thermal expansion coefficient for hTM. Thus,
amplitude measurements of TM and TL effects allow
quantitative access to thermal, optical, and mechanical
properties of the material.
In order to ensure the accuracy and repeatability of the
measurements, several TL and TM transients were
recorded at room temperature. The accuracy of the
measurements was then evaluated using the standard
deviation of the measurements with a 90% confidence
interval. The determined parameters, D and hj, reported
in this study are then the average of all the repeated
measurements within 90% confidence levels.
The temperature dependence of D and hj were
obtained by performing TL and TM measurements
from room temperature up to 170 8C. The experiments
were performed using a heating rate of 0.5 8C/min.
Each consecutive excitation time interval was 30 s,
which was an adequate delay to obtain the complete
TL or TM signal relaxation between each measure-
ment. The TL and TM transients were fit to the models,
and the resulting parameters are shown in Figs. 4 and
5. Figure 4a presents the temperature dependence of
the thermal diffusivity, D(T), obtained using TL and TM
for PC and PMMA. The D(T) shows a slight decrease
with temperature below 150 8C for PC and 75 8C for
PMMA. The thermal diffusion varies between 1.82 3
107 m2 s1 and 1.48 3 107 m2 s1 for PC and 0.88 3
107 m2 s1 and 0.84 3 107 m2 s1 for PMMA. Large
D(T) variations are observed near the glass transition
temperatures. Note the difference between the onset of
the transition observed on the thermal diffusivity data
for PC as measured using TL and TM results. This
could be a result of the temperature dependence of the
physical properties of the sample near the glass
transition.
The thermal conductivity, k(T), can be determined by
independently measuring the specific heat (Cp) and the
mass density as a function of temperature using the
relation k(T) = q(T)Cp(T)D(T). The volumetric thermal
expansion coefficients of these polymers at room
temperature are on the order of 2 3 104 K1 and around
10% larger near the glass transition. Thus, the variations
in the volumes in the considered temperature interval
here are less than 2% for both samples. Also, the mass
TABLE I. Physical properties of PC (L = 2.3 mm) and PMMA thicknesses, the TL amplitudes normalized by the
(L = 2.0 mm) at room temperature. thickness, hTLP1 L1, are slightly different. The differ-
ence is a consequence of the combined effects leading
PC PMMA
to the lens signal, i.e., the thermo-optic effect, thermal
7 2
D (10 m s ) 1
1.8 6 0.1 0.8 6 0.1 expansion, and the stress-optic effect, which present a
hTL Pe1 L1 (103 W1 m1) 4.6 6 0.5 0.5 6 0.1 complex dependence with thickness.39 If the thickness
hTM Pe1 (103 W1 m1) 2.8 6 0.5 —
q (kg m3) 1201 6 4 1198 6 4
is larger than the radius of the region affected by the
Cp (J Kg1 K1) 1320 6 45 1650 6 50 thermoelastic effect, the TL plane–strain approximation
k (Wm1 K1) 0.28 6 0.02 0.17 6 0.01 could be safely employed.
Ae @514.5 nm (m1) 6.3 6 0.3 3.0 6 0.2 The temperature dependence of the optical path
m44 0.414 0.343
n 1.584 6 0.001 1.480 6 0.001 change (ds/dT)TL can be calculated from hTL(T) using
(ds/dT)OI (106 K1) 2.9 6 0.1 1.0 6 0.1 Eq. 4. The optical absorption coefficients of the samples
(ds/dT)TL (105 K1) 13.0 6 0.9 1.8 6 0.2 were determined in the same temperature range by
dn/dT (105 K1) 10.1 6 0.8 10.6 6 0.9
aT (105 K1) 6.6 6 0.9 7.2 6 0.9
measuring the transmission at 514.5 nm, and the results
u (105 K1) 5.7 6 0.9 3.0 6 0.6 were found to be approximately constant with tempera-
DSO (105 K1) 2.9 6 0.3 8.7 6 0.9 ture from 25 to 150 8C for PC and 25 to 75 8C for PMMA
Tg (8C) 150 6 2 83 6 2 (Table I). Using k(T) and / = 1 for both samples, (ds/
dT)TL(T) was calculated, and the results are presented in
Fig. 6a. The values found at room temperature are listed
density can be considered approximately constant in our in Table I.
calculations for temperatures below 150 8C for PC and The parameter hTM(T) is related to thermal conduc-
75 8C for PMMA. Cp(T) and k(T) are shown in Fig. 4b. The tivity k(T) and linear thermal expansion coefficient
mass densities measured at room temperature are listed aT(T) of the sample by Eq. 1. As an example, we
in Table I. Cp(T), k(T) increase monotonically within the calculated the thermal expansion of PC using the
considered temperature interval. measured hTM (T) and k(T), and the results are
Figure 5 shows the result of the temperature presented in Fig. 6b. The Poisson ratio was assumed
dependence of the TL and TM signals amplitudes to be constant within this temperature range (Table I).
normalized by the excitation power, hj/Pe. The ampli- aT(T) determined from the TM measurements and
tudes are strongly affected near the glass transitions. measured using a commercial dilatometer are in good
The temperature derivative of hj(T) has been used to agreement. The linear thermal expansion coefficient
calculate the glass transitions in previous works16,17 for the PMMA sample was found to be approximately
and here yielded Tg = (150 6 2) 8C for PC and Tg = (83
constant below the glass transition.
6 2) 8C for PMMA. Note that for the samples of different

FIG. 4. Temperature dependence of the (a) thermal diffusivity and (b)

thermal conductivity of the polymer samples. The inset in (b) shows the FIG. 5. Temperature dependence of (a) TL amplitude, hTL/Pe, and (b)
specific heat. TM amplitude hTM/Pe.

APPLIED SPECTROSCOPY 781


FIG. 6. Temperature dependence of (a) temperature coefficient of
optical path length, (ds/dT)TL; (b) linear thermal expansion coefficient,
aT, and thermal coefficient of the electronic polarizability, u; and (c) the
temperature coefficient of refractive, dn/dT. The uncertainties in the
calculations of these parameters are less than 15%.
Regarding (ds/dT)TL, the subscript TL is necessary
here to distinguish this from the ds/dT measured with the
optical interferometer, (ds/dT)OI. (ds/dT)TL accounts for
the stress effects due to the nonuniformity of the
excitation laser beam. In the case of plane–strain
approximation,39 (ds/dT)TL can be written as
 
ds dn n 3 Y aT
¼ þ ðqjj þ 3q? Þ ð6Þ
dT TL dT 4ð1  mÞ
in which dn/dT is the temperature coefficient of refractive
index, n is the refractive index, Y is the Young’s modulus,
and qjj and q? are the stress-optical coefficients parallel
and perpendicular to the beam direction, respectively.
As a consequence of the temperature profile across the
sample, thermal stress effects can be generated, giving
rise to the second term in Eq. 6. This term is much
smaller than dn/dT in many systems and can be
omitted.17,39
An optical interferometer was employed to determine
the temperature dependence of the (ds/dT)OI. In this
method,41 the temperature change is homogeneous
throughout the sample, eliminating any stress effect
during heating. The interference pattern is detected as
described in detail elsewhere.41 A He–Ne laser at
632.8 nm was used as the optical source, and the sample
was heated using the same furnace used in the TL–TM
measurements. (ds/dT)OI values were approximately
constant (,5% variation) in the temperature range
below the glass transition for both samples, yielding
782 Volume 68, Number 7, 2014
(2.9 6 0.1) 3 106 K1 for PC and (1.0 6 0.1) 3 106 K1 for
PMMA. These values are very small compared with
(ds/dT)TL, indicating the competition between the nega-
tive dn/dT and aT. In fact, (ds/dT)OI can be written as41
 
ds dn
¼ þ naT ð7Þ
dT OI dT
Using aT(T) for both samples, and n as given in Table I,
dn/dT was calculated for PC, and the results are
displayed in Fig. 6c. The variation of aT(T) between 25
and 75 8C for PMMA was less than 5%, and it was
considered constant in the calculation. Additionally, the
difference between (ds/dT)OI and (ds/dT)TL can be used
to calculate thermo-optical properties for the sample.
These parameters can be related as
   
ds ds
 ¼ DSO  naT ð8Þ
dT TL dT OI
The stress-optic parameter is DSO = n3Y aT(qjj þ 3q?)/4(1
 m). Using the parameters listed in Table I, we estimated
DSO  2.9 3 105 K1 for PC and DSO  7.6 3 105 K1 for
PMMA at room temperature. In addition, dn/dT is related
to the temperature coefficient of the electronic polariz-
ability / by17
dn ðn 2  1Þðn 2 þ 2Þ
¼ ð/  3aT Þ ð9Þ
dT 6n
The negative values of dn/dT show that the expansion
term on the right side of Eq. 9 is dominant over the
electronic polarizability. The temperature dependence of
/(T) is presented in Fig. 6b for PC.
CONCLUSIONS
We propose a quantitative method for the in situ
evaluation of thermal, optical, and mechanical properties
of polymers. The thermal lens and thermal mirror
methods are used as a concurrent photothermal tech-
nique. This combined method was used to investigate
polymers as a function of temperature, from room
temperature up to 170 8C. A complete set of thermal,
optical, and mechanical properties of polycarbonate and
poly (methyl methacrylate) samples were obtained. The
concurrent method presented here can be a useful tool
for in situ characterization of semitransparent materials,
where fast and non-contacting measurements are
required.
ACKNOWLEDGMENTS
The authors are thankful to the Brazilian Agencies CAPES, CNPq,
FINEP, and Fundação Araucária for the financial support of this work.
NGCA also thanks Fulbright and CAPES for financial support under the
process BEX 17572/12.
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