1. Introduction
Online determination of substances in industrial processing liquids can facilitate
continuous processing,
enable real-time information flow, save power energy, and improve material use,
which are high on the list of priorities of industrial manufacture requiring
concentration measurements and process control. Thanks to well-developed techniques
and inexpensive devices, optical and ultrasound measurements have been successfully
applied to these tasks. However, optical techniques usually measure optical
parameters (absorption, scattering, or refractive index) and ultrasound determines
acoustic speed or attenuation. Moreover, simultaneous monitoring of both optical and
acoustic properties necessitates two or more sensing systems [
1M. Tormanen, J. Niemi, T. Lofqvist, and R. Myllyla, “Pulp consistency determined by a
combination of optical and acoustical measurement
techniques,” Meas. Sci. Technol.
17, 695–702
(2006). [CrossRef]
Q. Zhu, D. Sullivan, B. Chance, and T. Dambro, “Combined ultrasound and near infrared
diffused light imaging in a test object,”
IEEE Trans. Ultrason. Ferroelectr. Freq. Control
46, 665–678
(1999).
C. A. DiMarzio and T. W. Murray, “Medical imaging techniques combining
light and ultrasound,” Subsurf. Sens.
Technol. Appl.
4, 289–309
(2003).
V. Cunningham and H. Lamela, “Optical and optoacoustic measurements of
the absorption properties of spherical gold nanoparticles within a highly
scattering medium,” Opt. Laser
Technol.
42, 769–774
(2010). [CrossRef]
J. Niemi, T. Lofqvist, and P. Gren, “On a new sensing strategy using a
combination of ultrasonic and photoacoustic
techniques,” in Proceedings of IEEE Conference on
Ultrasonic Symposium
(IEEE, 2006), pp.
1797–1800.
S. Y. Emelianova, S. R. Aglyamov, J. Shah, S. Sethuraman, W.
G. Scott, R. Schmitt, Motamedi Massoud, A. Karpiouk, and A. A. Oraevsky, “Combined ultrasound, optoacoustic and
elasticity imaging,” Proc. SPIE
5320, 101–112
(2004).
–
7Y. Shen, Z. Lu, S. Spiers, H. MacKenzie, H. Ashton, J. Hannigan, S. Freeborn, and J. Lindberg, “Measurement of the optical absorption
coefficient of a liquid by use of a time-resolved photoacoustic
technique,” Appl. Opt.
39, 4007–4012
(2000). [CrossRef]
].
Naturally, the more parameters a technique can measure, the more information it
reveals of the studied material. To that end, a hybrid technique was developed
utilizing a single optical, electrical, and ultrasonic sensor to measure optical
intensity, electrical impedance, and ultrasonic speed in order to determine
ingredient concentrations in liquids [
8A. Kimoto and T. Kitajima, “An optical, electrical and
ultrasonic layered
single sensor for ingredient measurement in
liquid,”
Meas. Sci. Technol.
21, 035204 (2010).
]. This
sensor comprises a pair of optical devices, a pair of electrodes, and a pair of
ultrasonic devices.
We have previously proposed a hybrid technique utilizing a pair of laser-detectors to
determine optical parameters and acoustic attenuation in turbid suspensions. This
technique has been successfully applied
to the measurement of fiber and fines consistencies in paper pulp [
9Z. Zhao and R. Myllylä, “Measuring the optical parameters of
weakly absorbing, highly turbid suspensions by a new technique:
photoacoustic detection of scattering light,”
Appl. Opt.
44, 7845–7852
(2005). [CrossRef]
Z. Zhao, M. Törmänen, and R. Myllylä, “A preliminary
measurement of fibres and fines
in pulp suspensions by the scattering photoacoustic
technique,” Meas. Sci. Technol.
17, 128–134
(2006). [CrossRef]
–
11Z. Zhao, M. Törmänen, and R. Myllylä, “Backward-mode photoacoustic transducer
for sensing optical scattering and ultrasonic attenuation: determining
fraction consistency in pulp suspensions,”
Meas. Sci. Technol.
21, 025105 (2010). [CrossRef]
]. In this study, we explore a new hybrid
technique based on time-resolved photoacoustics (TR-PA), capable of measuring
simultaneously the optical, acoustic, and thermal-acoustic transformation properties
of an absorbing liquid. It is well known that the photoacoustic (PA) effect [
12A. C. Tam, “Applications of photoacoustic sensing
techniques,” Rev. Mod. Phys.
58, 381–431
(1986).
] is the phenomenon of acoustic wave
generation by a pulsed laser or a modulated light source. When a pulsed laser
irradiates an absorbing material, the optical energy of the laser is absorbed by the
absorbing material, where it transforms into heat energy, causing a thermal
expansion of the illuminated region. Owing to inertial effects within the material,
this type of modulated thermal expansion causes the illuminated region to extend and
compress. As a result of this action, an acoustic wave is generated. The thus
produced PA wave propagates out from the generation region (PA source) and can
subsequently be detected by an ultrasonic transducer. Hence, there are three
processes from PA generation to detection:
optical energy absorption, thermal
expansion, and acoustic propagation. With its custom-tailored design, our new
apparatus, consisting only of a laser-detector pair, has the ability to
simultaneously measure the optical
absorption coefficient,
thermal-acoustic transformation
coefficient, and acoustic speed in an absorbing liquid. To the authors’
knowledge, no other publication exists that describes
the simultaneous measurement of these
three parameters.
The developed technique is particularly suitable for online measurement of
constituent concentrations in liquid mixtures, as the three physical
parameters (optical absorption,
acoustic speed, and thermal-acoustic transformation) can be quickly and
simultaneously determined by analyzing recorded time-resolved PA signals. No doubt,
this technique will prove very useful for the chemical, food, and paper industries,
as well as for environmental protection. For instance, it could be used in the
pulping industry to determine lignin, sugar, and dissolved alkaline contents in
cooking liquids. It may also be applied by the offshore oil industry to measure
concentrations of dissolved oil, salts, and oil field chemicals in water.
2. Theoretical Aspects
When a pulsed laser beam irradiates a homogeneously absorbing medium, as shown in
Fig.
1(a), the optical energy is
absorbed in the illuminated region of the medium and then transformed into heat in
the thermal de-exciting mechanism [
12A. C. Tam, “Applications of photoacoustic sensing
techniques,” Rev. Mod. Phys.
58, 381–431
(1986).
].
Transient heat, produced by thermal expansion of the heated volume, will generate an
initial stress. Since thermal diffusion from the heated volume can be ignored during
nano- or microsecond laser pulses, the initial stress distribution equals that of
the absorbed optical energy fulfilling the stress confinement condition [
13A. Oraevsky, S. Jacques, and F. Tittel, “Measurement of tissue optical properties
by time-resolved detection of laser-induced transient
stress,” Appl. Opt.
36, 402–415
(1997). [CrossRef]
]. This stress is relaxed by generating an
outward propagating acoustic wave. If the light beam diameter
is much larger than the optical penetration depth
(i.e., the thickness of the heated volume) in the
absorbing medium, the PA source (i.e., the heated volume) is planar and the PA wave
propagates along the depth direction of the medium. The acoustic pressure at the
depth of
can be described by
where
is the radiant exposure of the laser pulse at the
medium surface,
the absorption coefficient,
the thermal expansion coefficient,
the specific heat, and
the acoustic speed in the medium.
Fig. 1. Principle of time-resolved photoacoustic measurement: (a) radiation and
detection, (b) measurands of received signals.
Figure
1(b) shows a typical signal
recorded by a wideband ultrasonic detector used to receive acoustic waves at depth
. This signal can be described as
, where
is a system constant and
is a function of detector response. Substituting
Eq. (
1) and doing the
logarithm, the formula takes the form
where
is the amplitude of the signal which is not a
function of time
,
is a system constant including the radiant exposure
of the laser pulse at the medium surface, and
is the thermal-acoustic transformation coefficient
(so-called Grüneisen coefficient). Equation (
2) describes a linear relationship between the semilogarithm
and
, meaning that
can be deduced from the
linear slope. It is worth mentioning
that
is
self-calibrated, as it is unaffected by
the system constant, laser energy fluctuation and the response function of the
detector. Acoustic speed
can be easily measured by
, where
is the propagating time of the acoustic wave from
the medium surface to the detector. Hence, the optical absorption coefficient
of the medium can be deduced after knowing
. To compute
from the signal amplitude
, requires prior determination of detector response
and detecting system constant.
In general, the detector response
is a function of acoustic frequency. In the case of
PA generation of a planar source, the center frequency of the generated PA wave can
be calculated as
for an absorbing medium fulfilling the stress
confinement condition [
14W. Sigrist, “Laser generation of acoustic waves in
liquids and gases,” J. Appl. Phys.
60, R83–R121
(1986). [CrossRef]
]. The detector
response can therefore be written as
, a function of optical absorption coefficient. In
this study, very small quantities of an absorbing material
(
) were added into distilled water to make
calibration solutions, allowing
of the detection system to be
calibrated:
In Eq. (
3),
is the signal amplitude produced in calibration
solutions and
is the known Grüneisen coefficient of water.
Finally,
of absorbing medium can be calculated by measuring
signal amplitude, optical absorption
coefficient, and calibration curve
.
In summary, acoustic speed and optical absorption coefficient can be deduced directly
from the time-of-flight of a time-resolved PA signal and its front profile. The
thermal-acoustic transformation coefficient, on the other hand, can be calculated
from signal amplitude, optical
absorption coefficient, and the
calibrated curve of the measurement
system, determined by a suitable calibration liquid. If the
transducer has a flat
response in the studied acoustic
frequency range, the relative value of
the thermal-acoustic transformation coefficient can be deduced without calibration
from optical absorption and signal amplitude.
3. Experimental Apparatus and Samples
Figure
2 shows the scheme of the
experimental apparatus used for measuring liquid samples. A tunable laser (Opolette
HE 355 II, OPOTEK Inc.) with a 5 ns pulse duration and a 355 nm pumping
wavelength is used as the exciting source to produce PA waves. To satisfy the
requirement of generating a planar PA source, optical lenses expand the laser beam
to a diameter of 20 mm, before it passes through an optical aperture with a
diameter of 15 mm. A rough glass slide is put in the optical path for further
smoothing the optical energy distribution in the beam’s cross-section, before
it enters a cuvette where the sample is placed. A plane of fused silica with a
thickness of 5 mm functions as cuvette window to produce a limiting boundary
condition for highly-efficient PA generation. Measuring 1 cm in thickness, the
cuvette is capable of eliminating the effects of acoustic diffraction and
attenuation. Aligned with the excited laser beam is a homemade detector, combining a
piezoelectric PVDF transducer with a preamplifier. This detector is acoustically
coupled to the back surface of the cuvette by a drop of silicon oil. The thickness
of the PVDF foil is 52 µm, the gain of the preamplifier is 40 dB, and
the 6 dB bandwidth is about 200 kHz—5 MHz. To prevent the
laser beam from directly irradiating the detector surface when using a sample with
low optical extinction, the back surface of the cuvette is covered by a reflecting
layer of aluminum film with a thickness of 150 nm. A thermocouple is inserted
into the cuvette for monitoring the temperature of the solution. In addition, a
photodiode is used to monitor the energy fluctuation of the laser pulses. The output
from the detector is connected to a
two-channel digital card (PCI-1250, NI, sampling at
) in a PC and, to compensate for the energy
fluctuation effect of the laser pulses, the output is divided by the amplitude of
the photodiode’s output. One hundred twenty-eight compensated signals are
averaged by LabView software to decrease random noise in the detection channels and
the amplitude and wave-shape of the averaged signals are recorded in the PC for
postprocessing.
Fig. 2. Experimental scheme of time-resolved photoacoustic measurement.
As samples, this study used aqueous solutions of potassium chromate
(
) and mixtures of potassium chromate and glucose,
because their properties are well known. Potassium chromate has a very
high optical absorption coefficient at
355 nm (about
at a concentration of
[
13A. Oraevsky, S. Jacques, and F. Tittel, “Measurement of tissue optical properties
by time-resolved detection of laser-induced transient
stress,” Appl. Opt.
36, 402–415
(1997). [CrossRef]
]).
Moreover, potassium chromate solutions do not fluoresce and their optical properties
are not altered by strong laser
exposure. As a result, potassium
chromate is suitable for the
calibration of the PA measurement system and for the quantitative PA detection of
absorption coefficients in solutions. Glucose, on the other hand, exhibits
considerably weaker optical absorption characteristics at this
wavelength. However, it will change the
thermal parameters [
15H. MacKenzie, H. Ashton, S. Spiers, Y. Shen, S. Freeborn, J. Hannigan, J. Lindberg, and P. Rae, “Advances in photoacoustic noninvasive
glucose testing,” Clinical Chem.
45, 1587–1595
(1999).
,
16Z. Zhao, “Pulsed photoacoustic techniques and
glucose determination in human
blood and tissue,” doctoral thesis (Acta
Universitatis Ouluensis, Series C 169,
2002).
] and density of the solutions it is added to.
4. Experiments and Results
Before measurements, all liquid samples were prepared and put on the laboratory table
at room temperature (22 °C) and the experimental apparatus was preheated
for 30 minutes. The experiments included three steps. Potassium chromate solutions
with concentrations from 0.02 wt. % to 0.1 wt. % were successively loaded into the
cuvette. Then, to make glucose solutions, varying amounts of glucose (0.2 g,
0.4 g, 0.6 g, 0.8 g, and 1 g, respectively) were added into
10 ml of potassium chromate solutions with a concentration of 0.02%. Potassium
chromate was used here as background absorber in the glucose solutions for PA
generation, because glucose and distilled water have little optical absorption at
the investigating wavelength—355 nm. Finally, five mixed solutions, each
with a different concentration of potassium chromate and glucose, were measured. In
every measurement, the signal amplitude was recorded ten times to calculate the
standard deviation of the amplitude. The sample was then sucked out by a plastic
pastette and the cuvette was washed twice using distilled water, before a new sample
was loaded. When measured, the temperature difference, due to room temperature
fluctuations during the experiment, was less than 0.3 °C in all
samples.
Figure
3 shows a typical TR-PA signal
recorded in a
solution. In agreement with Eq. (
2), the inserted graph, drawn in the
semilogarithm scale, illustrates good linearity at the signal front. As the
concentration increases, so does the recorded
signal amplitude, while the arriving time of the amplitude remains almost unchanged.
Figure
4 illustrates the measurement
result. It demonstrates an optical absorption coefficient of
and an acoustic speed of
for a 0.02%
solution. Both of these values are nearly identical
to those presented in [
13A. Oraevsky, S. Jacques, and F. Tittel, “Measurement of tissue optical properties
by time-resolved detection of laser-induced transient
stress,” Appl. Opt.
36, 402–415
(1997). [CrossRef]
]. With increasing
concentration, the absorption coefficient grows linearly with a huge slope rate,
whereas acoustic speed is unaffected within the measurement error range. As the
solutions were highly diluted, their Grüneisen coefficients should be identical
and equal to that of water (
at 22 °C). Based on this consideration,
the
of the measurement system can be calculated for
solutions with different concentrations (or optical absorption), as shown in
Fig.
4. Doing a polynomial fit to
these data allowed us to obtain a calibrated curve for computing the Grüneisen
coefficient of the current measurement system:
Fig. 3. Typical TR-PA signals recorded in solutions with different concentrations
(the inserted graph is shown in the semilogarithm axis).
Fig. 4. Experimental results of calibration
solutions (standard deviations
are smaller than the marks).
Figure
5 monitors how the three
parameters changed with glucose concentration in aqueous solutions containing 0.02%
. As seen, a 1% increase in glucose concentration
increased the Grüneisen coefficient by about 3.4% and acoustic speed by 0.26%.
These values are in good agreement with previously published data [
7Y. Shen, Z. Lu, S. Spiers, H. MacKenzie, H. Ashton, J. Hannigan, S. Freeborn, and J. Lindberg, “Measurement of the optical absorption
coefficient of a liquid by use of a time-resolved photoacoustic
technique,” Appl. Opt.
39, 4007–4012
(2000). [CrossRef]
,
16Z. Zhao, “Pulsed photoacoustic techniques and
glucose determination in human
blood and tissue,” doctoral thesis (Acta
Universitatis Ouluensis, Series C 169,
2002).
].
The error bars for the relative change of the Grüneisen coefficient in response
to concentration increase are mainly caused by fluctuations in laser pulse energy
and the error in measuring the
absorption coefficient. Yet another contributing factor is temperature; the
Grüneisen coefficient of the solutions increased by 1.3% when room temperature
increased by 0.3 °C [
13A. Oraevsky, S. Jacques, and F. Tittel, “Measurement of tissue optical properties
by time-resolved detection of laser-induced transient
stress,” Appl. Opt.
36, 402–415
(1997). [CrossRef]
]. In
addition, the absorption coefficient decreased about 0.72%, due to the diluting
effect of glucose on potassium chromate.
Fig. 5. Relative change of the three parameters with glucose concentration (error
bars for acoustic speed and absorption coefficient are smaller than the
marks).
Figure
6 gives the experimental result of
the three parameters obtained from five mixed solutions, consisting of
and glucose. Shown in square brackets under the
horizontal axis are the used concentrations (for example, [0.091_9.1], indicating a
mixed solution consisting of 0.091% of potassium chromate and 9.1% of glucose). It
is easy to understand that the values of the three parameters increase with
concentration and Table
1 illustrates
the relative increase of each parameter. For comparison, the table also lists the
results contributed by the sum of the
solution and glucose solution (calculated from the
data presented in Figs.
4 and
5). It is evident that the result in
Fig.
6 is practically identical to
the sum of the results in Figs.
4 and
5.
Fig. 6. Measurement results of the three
parameters obtained from mixed
solutions containing and glucose.
Table 1. Comparing Relative Changes in the Three Parameters Deduced from
Fig.
6 and the Sum of
Figs.
4 and
5 | (%) | (%) | (%) |
| [_glucose] concentration (%)
in mixed solutions | Fig. 6 | Figs. 4
& 5 | Fig. 6 | Figs. 4
& 5 | Fig. 6 | Figs. 4
& 5 |
| [0.02_2] | 0 | 0 | 0 | 0 | 0 | 0 |
| [0.038_3.8] | 106 | 98 | 0.39 | 0.49 | 11 | 7 |
| [0.057_5.7] | 202 | 200 | 0.73 | 0.97 | 19 | 13 |
| [0.074_7.4] | 299 | 292 | 1.15 | 1.43 | 21 | 19 |
| [0.091_9.1] | 393 | 384 | 1.57 | 1.87 | 29 | 24 |
5. Discussion
Although the constituents of most processing liquids are known, determining the
concentration of each constituent may require real-time measurements. This became
our motivation to develop the multiparameter measurement technique presented in this
study. Table
1 demonstrates that
and glucose concentrations in mixed solutions can
be deduced by measuring three parameters, provided that the effects of
and glucose on these parameters are determined
beforehand. In general, this technique is applicable to absorbing liquids consisting
of three constituents in which no chemical reactions take place. The technique
allows determining the concentration of each constituent, if they all
contribute to optical
absorption, acoustic speed, or
thermal-acoustic transformation with a
different weight factor.
Our experiment demonstrates that the absorption coefficient can be deduced with
measurement error no larger than 3% (when measuring a sample three times), without
calibration. It is worth mentioning that the result remains accurate, even if only a
part of the signal’s front profile satisfies the exponential distribution.
This offers the extra benefit that a high absorption coefficient can be correctly
measured by a transducer whose frequency bandwidth does not cover the higher
frequency components of the PA wave produced in the sample (of course, the deduced
Grüneisen coefficient is not
correct in this case). Dominating error sources in the absorption coefficient
measurement are the following: 1) energy fluence in the cross-section of the
laser beam is not strictly homogeneous, 2) the laser beam is probably not well
collimated, and 3) the detector and the laser beam are not exactly aligned.
Acoustic speed was deduced by measuring the arrival time of a PA amplitude signal
with a measuring error of up to 0.3%. Errors arise mainly from a slight difference
in the transducer’s response to a wide range of PA frequencies and a possible
change of acoustic coupling between the detector and cuvette wall when uploading and
downloading samples during the measurement.
The measurement error of thermal-acoustic transformation coefficient in this study is
mainly due to an error in determining the absorption coefficient or calibration
curve and to fluctuations of laser pulse energy and the temperature of the solution.
In contrast to measuring the absorption coefficient and acoustic speed, correctly
determining the thermal-acoustic transformation coefficient sets higher requirements
for the experimental setup as it also needs to measure the amplitude value of the PA
pressure. In practice, the pressure amplitude is measured by the amplitude of the PA
signal, but it must be noted that the two are not identical. Although signal
amplitude is proportional to pressure amplitude, it is also related to the response
sensitivity and frequency bandwidth of the detector, energy fluctuation of laser
pulses, as well as to acoustic diffraction and attenuation within the sample. If the
frequency spectrum of a PA wave exceeds the detector bandwidth, the PA signal
amplitude will be cut and is no longer proportional to the pressure amplitude. In
this study, the lower and upper frequencies of the detector's 6 dB bandwidth
are about 200 kHz and 5 MHz,
respectively,
corresponding to optical absorption coefficients of
and
in aqueous
solutions. This is the reason why
solutions with concentrations from 0.02% to 0.1%
were used in the measurement (the
absorption coefficients of these solutions are within the range mentioned above).
Moreover, since the detector response in the 6 dB bandwidth is not flat with
frequency change, it tends to modulate the signal amplitude, following changes in
optical absorption in the solution. The
effect of detector response and the
effect of the system constant on signal amplitude were jointly compensated for by
using a calibration curve (see
in Fig.
4). This eliminates the need to measure the detector response by other
acoustic instruments. It is worth mentioning that, in the experimental condition
reported here, the diffraction parameter
was larger than 0.62 and the acoustic frequencies
were lower than 5 MHz, allowing acoustic diffraction and attenuation to be
ignored [
13A. Oraevsky, S. Jacques, and F. Tittel, “Measurement of tissue optical properties
by time-resolved detection of laser-induced transient
stress,” Appl. Opt.
36, 402–415
(1997). [CrossRef]
].
Finally, determining three parameters simultaneously in liquid necessitates using a
purely absorbing liquid, because Eq. (
1) only applies to purely absorbing materials. In the case of turbid
samples, the TR-PA technique, as described above, has the capacity to measure the
optical extinction coefficient (including the optical absorption and scattering
coefficients) and acoustic speed, but fails at measuring the thermal-acoustic
transformation coefficient, due to backscattering of the incident optical beam.
However, if the laser is wavelength-tunable such that the optical absorption of the
sample is much stronger at some wavelengths than optical scattering, the technique
is still capable of correctly deducing the thermal-acoustic transformation
coefficient. This is because the extinction coefficient approximately equals the
absorption coefficient and backscattering can be ignored. Another benefit of
applying a tunable laser is that it probably tunes the frequencies of the generated
PA waves into the bandwidth of the detector. This not only expands the application
range of the sample category, but also lowers detector requirements, since there is
a trade-off between detector bandwidth and amplifying gain.
6. Conclusion
A hybrid technique was developed to simultaneously measure the optical absorption
coefficient, acoustic speed, and thermal-acoustic transformation coefficient in an
absorbing liquid, based on the TR-PA detection of the profile, amplitude, and flight
time of PA signals. Conducted experiments utilized potassium chromate as absorber
and glucose as nonabsorbing substance in mixed solution samples. The current
experimental setup achieves measurement errors of 3%, 0.3%, and 8% in determining
the optical absorption coefficient, acoustic speed, and thermal-acoustic
transformation coefficient, respectively. The setup is suitable for measuring
absorbing liquids with an absorption coefficient in the range of
to (the range is limited by the detector bandwidth,
not by the technique itself). Our experimental results show that, in mixed
solutions, the value of each of these parameters is approximately equal to the sum
value of the same parameter measured in a potassium chromate solution and a glucose
solution. Hence, potassium chromate and glucose concentrations in mixed solutions
can be deduced by measuring these parameters in constituent and mixed solutions. To
sum up, the technique described here has the ability to monitor three constituent
concentrations in an absorbing liquid, provided that these substances have different
optical absorption, acoustic speed,brvgf or thermal-acoustic transformation
properties. At the next step, the apparatus will be further improved to increase its
measurement accuracy. Then it will be applied to measuring actual industrial
processing liquids.