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Journal of Food Engineering 76 (2006) 250–255

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Dielectric study of milk for frequencies between 1 and 20 GHz


a,*
A.C. Nunes , X. Bohigas b, J. Tejada c

a
Department of Physics, University of Rhode Island, Kingston, NY 02881, United States
b
Departamento de Fı́sica i Enginyeria Nuclear, Universitat Politècnica de Catalunya, Diagonal, 647 08028 Barcelona, Catalonia, Spain
c
Departamento de Fı́sica Fonamental, Universitat de Barcelona, Diagonal, 647 08028 Barcelona, Spain

Received 4 June 2004; received in revised form 5 April 2005; accepted 25 April 2005
Available online 1 July 2005

Abstract

The complex permittivity of milk at room temperature (17–20 C) was studied over the frequency range of 1–20 GHz. UHT
whole, low fat and skim milk were examined, fresh from the container, and over a period of two weeks while they were allowed
to spoil at room temperature. In addition, the spectrum of whole milk at various dilutions was also measured. Both the real and
imaginary parts of the permittivity were found to be smooth, slowly varying functions of frequency over this range. The Debye rela-
tion, with an additional term for ionic conduction losses was fitted to the data, and six parameters were extracted. The variation of
these parameters with fat content and dilution suggests that they may be useful to roughly determine the milkÕs content in terms of
groups of materials (ionic compounds, fats, and carbohydrates and proteins). Spectra also vary significantly with spoilage, but anal-
ysis is complicated by concerns of physical (phase separation) in addition to chemical changes.
 2005 Elsevier Ltd. All rights reserved.

Keywords: Microwave; Milk; Spoil; Permittivity; Ionic loss; Dielectric properties; Composition

1. Introduction microwaves in characterizing the quality of various


foods, including measurement of salt content (Kent &
The response of substances to electromagnetic radia- Anderson, 1996; Shiinoki, Motouri, & Ito, 1998), added
tion is complex, and dependent upon many parameters, water content of processed meat (Kent & Anderson,
including temperature, physical state, and the chemical 1996; Kent, Knöckel, Daschner, & Berger, 2001), and
composition of the material. The microwave range of possible detection of bacteria in milk (Váczy & Semberg,
the spectrum (frequencies between 0.5 and 300 GHz) is 2003). Use of microwaves on food is attractive because
increasingly exploited in probing fundamental questions of the rapidity of treatment and/or measurement, ease
in physics and chemistry. Microwaves also find more of use, and the fact that it can potentially be used on
general, practical application for treating and character- foods in optically opaque sealed containers. To date,
izing foods. They are used in the pasteurization and most investigations have employed radiation of fre-
cooking of foods, typically at frequencies of 0.915 and quency less than 10 GHz partly due to the lack of read-
2.450 GHz (Herve, Tang, Luedecke, & Feng, 1998; ily available higher frequency sources.
Wang, Wig, Tang, & Hallberg, 2003). There are also Our laboratory at the University of Barcelona has
many papers reporting investigations of the use of traditionally employed microwaves in studies of mag-
netic materials, and has instruments capable of measur-
ing dielectric properties of materials over a wide range of
frequencies (Amigó, Hernández, Garcı́a Santiago, &
*
Corresponding author. Tel.: +1 401 874 2048; fax: +1 401 874 2380. Tejada, 2003a, 2003b). Recognizing the potential value
E-mail address: acnunes@uri.edu (A.C. Nunes). of microwaves in fields beyond our own immediate

0260-8774/$ - see front matter  2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2005.04.049
A.C. Nunes et al. / Journal of Food Engineering 76 (2006) 250–255 251

scientific interests, and our responsibility to the broader 2.2. Instrument and procedures
community that ultimately supports us, we have decided
to set aside some instrument time for studies of ques- The instrument used to measure the complex permit-
tions of immediate practical importance. tivity of these materials was a Hewlett Packard 8510C
As a first step in this direction, we report here an Network Analyzer coupled to an 83651B Synthesized
investigation of the dielectric properties of milk (UHT, Sweeper, and an 8517B S-Parameter test set. The probe
skim, low fat, and homogenized whole milk) over the used was an Agilent coaxial probe, model 85070C. All
frequency range 1–20 GHz. Milk was chosen because modules but the probe have 50 GHz capability. The
it is an important dietary staple, and is easily handled probe limited the upper frequency to 20 GHz. The sys-
and prepared for microwave exposure. This is not meant tem was controlled by an Agilent program running un-
to be a definitive example of how microwaves will be der Windows.
used to characterize milk, but merely as an indication All measurements were made at room temperature
of the form such measurements might take, what the (17–20 C). Samples were allowed to reach equilibrium
data may look like, and what components of the milk before being tested (approximately 50 min). The temper-
may be most easily detected. ature of each sample and calibration standard (deionized
It should be noted that the instrumentation used in distilled water) was determined with a mercury labora-
this study was designed for scientific research. It is tory thermometer (1 degree graduations). All parts of
highly sophisticated, expensive, requires skilled person- the instrument (including the probe) were mechanically
nel to operate and maintain, and is not something many fixed to avoid subtle changes in instrument configuration
businesses would consider buying or using as part of or cable shape that might affect calibration. The samples
their processing protocols. It is hoped, however, that and calibration standard fluid (in a 100 or 50 ml beaker)
studies of this sort will identify a small number of dis- were brought to the motionless probe. Care was taken to
crete frequencies most sensitive to those specific charac- eliminate bubbles from the probe surface. The probe was
teristics of a product that a company may wish to washed with deionized distilled water and wiped between
monitor. A much simpler instrument, operating only each measurement. Tests demonstrated that beaker size
at those frequencies, would be cheap to build, would did not affect the shape of the spectra.
not require an operator with an advanced degree, and Standard calibration was performed with deionized
would permit rapid, on-line, monitoring of product distilled water, air, and a short as described in the instru-
quality. mentÕs userÕs manual. The calibration procedure re-
quired 1 to 112 min.
In spite of all precautions, a deterioration of the data
was sometimes observed over a period of 5–10 min for
2. Materials and methods
no apparent reason. This took the form of undulations
appearing in what should be a very slowly varying spec-
2.1. Sample preparation
trum. To minimize and monitor this effect, the instru-
ment was always calibrated just before making a
Three types of UHT milk, purchased from a local
measurement, and the spectrum of the calibration stan-
supermarket, were used in this study: skim, low fat,
dard was taken just before and just after that of each
and homogenized whole milk. The compositions listed
sample. This means that the instrument was calibrated
on the cartons are presented in Table 1.
roughly every 10 min or less.
In addition to measuring the spectra of each of these
fresh from the carton, other tests were performed. One
2.3. Theory
series of measurements was made on successive dilutions
of whole milk. Also, three samples were left at room
The response of any material to microwave radiation
temperature in parafilm covered beakers for nearly
is denoted by its complex permittivity, e = e 0  je00 , where
two weeks. Several spectra of these were measured over
e 0 is its real part, e00 is its imaginary component, both of
this period as the milk spoiled.
which are functions of frequency, and j = (1)1/2. The
major chemical constituent of milk, and indeed of most
food, is water. Water is a strongly polar solvent. The
Table 1 permittivity of a polar material, such as free water, is de-
Compositions of the three samples used in this study, in grams per scribed reasonable well by the Debye relation (Ryynä-
100 g of sample
nen, 1995):
Sample Protein Carbohydrates Fat Calcium Water e0  e0
e0 ðxÞ ¼ e01 þ S 212 and
Skim 3.20 4.70 0.30 0.13 92 1þx s ð1Þ
Low fat 3.15 4.65 1.55 0.121 91 00 ðe0S  e01 ÞðxsÞ
Whole 3.10 4.60 3.60 0.12 89 e ðxÞ ¼ .
1 þ x2 s2
252 A.C. Nunes et al. / Journal of Food Engineering 76 (2006) 250–255

The real part of the complex permittivity, e 0 (x), is asso- the fitting algorithm. We believe this to result from the
ciated with energy storage in the substance. The imagi- shortcomings of Eqs. (1) and (2) when used to describe
nary part e00 (x), reflects the ability of the sample to a complicated real-world system. Nonetheless, using
convert electromagnetic energy into thermal energy. In these functions with the milk spectra produced fits that
these expressions, x is the angular frequency of the radi- were not much worse than fits to the calibration stan-
ation, e0S is the real static (low frequency) permittivity, dard, therefore it was felt that increasing the complexity
e01 is the real permittivity at very high frequency, and of the fitting functions to attempt to extract more infor-
s = 1/(2pfR). The frequency fR is called the relaxation mation from the data was not warranted.
frequency, and is the value at which the dipole displace-
ment lags that of the driving field by p/2. At this fre-
quency, the imaginary part of the complex permittivity 3. Results and discussion
(energy absorption) reaches its maximum. For water,
this occurs between 10 and 20 GHz, depending upon Fig. 1 presents the spectra of the calibration standard
temperature. For water bonded to other molecules (pro- (deionized distilled water), and the three types of milk
tein, for example) the relaxation frequency is generally studied, measured between 1 and 20 GHz using steps
lower as relaxation frequency decreases with a decrease of 0.1 GHz. In Fig. 1a, the upper set of curves are the
in dipole mobility (Ryynänen, 1995). real e 0 (x), while the lower set present e00 (x). Solid lines
In addition to dipolar molecules, milk (along with are curves fitted to the data as described above. Fig.
nearly all organic fluids) contains free ions. Ionic con- 1b presents all measurements of e 0 (x), and e00 (x). Note
duction is another major contributing factor to the that as the milk fat content increases, the milk spectra
dielectric loses of liquid samples. At microwave frequen- depart further from the water spectrum. The real part
cies, it has been shown that the loss factor due to ionic of the spectrum of each sample e 0 (x), is quite similar
conduction varies with the reciprocal of the frequency
(Garcı́a, Torres, Prieto, & De Blas, 2001). This loss fac-
tor can be included in e00 (x) by the addition of such a
term:
ðe0S  e01 ÞðxsÞ r
e00 ðxÞ ¼ þ ; ð2Þ
1 þ x 2 s2 xe0
where e0 = 8.854 · 1012 F/m is the permittivity of free
space, and r is the conductivity of the sample (Metaxas
& Meredith, 1993). Note that this expression has only
three adjustable parameters r, s, and (e0S  e01 ), as only
the difference e0S  e01 , not the individual values of each
quantity can be determined by fitting Eq. (2) to a data
set.
Other species (proteins, carbohydrates, and smaller
organic molecules) also have dipole moments, meaning
that, when used to model real organic systems (with
many biomolecular components) Eqs. (1) and (2) should
have additional terms of the same form as shown, but
with parameters specific to the other species. In addi-
tion, species can interact, further complicating the pic-
ture. For this reason, Eqs. (1) and (2) are only
approximations. It is interesting that they describe these
experimental results as well as they do (see below).
In this study, these expressions for e 0 (x) and e00 (x)
were fit to their respective data independently using a
standard nonlinear least-squares method to find the best
values of e0S , e01 , (e0S  e01 ), s, and r. In doing so, it was
found that (e0S  e01 ), determined from the loss factor,
was often close to but significantly different from the dif-
ference of these parameters determined from the e 0 (x) Fig. 1. Measured microwave spectra of deionized distilled water, and
fresh UHT skim milk, UHT low fat milk, and UHT whole milk
data. Similarly, the two values of s obtained indepen-
(1 < f < 20 GHz). Solid lines in (a) result from fitting Eq. (1) to e 0 (x),
dently from the curves fit to the e 0 (x) and e00 (x) data and fitting Eq. (2) to e00 (x) data. (b) depicts raw data without fitted
were not in agreement within the errors generated by curves.
A.C. Nunes et al. / Journal of Food Engineering 76 (2006) 250–255 253

to that of water, and indeed, can be fit well by the Debye


relation (Eq. (1)). The imaginary part of the permittivity
of each milk sample, e00 (x), is significantly higher at the
lower frequencies than that of water, and is not well de-
scribed by the Debye relation alone (Eq. (1)). Inclusion
of ionic conduction losses (Eq. (2)) yields a significant
improvement in the fit. This is certainly due largely to
the presence of salts in the milk, as ionic conductivity
in solutions can be an important source of loss at fre-
quencies in the low GHz range and below (Ryynänen,
1995).
The departure of the spectra of the three milk samples
from that of water is perhaps clearer when plotted as
Fig. 3. Spectra of the low fat milk sample left at room temperature
e0 ðxÞ=e0W ðxÞ and e00 ðxÞ=e00W ðxÞ, where e0W ðxÞ and e00W ðxÞ
(17–20 C) in parafilm covered beakers, as a function of time. The
are the real and imaginary parts of the water spectrum, numbers indicate days after opening the carton. Spectra of the other
respectively. This is presented in Fig. 2. samples are similar. During this time, the milk became noticeably
Fig. 3 depicts the spectra of one of the milk samples spoiled.
as a function of time left on a shelf at room temperature
(17–20 C). The behavior of the spectra of the other two
weeks after being opened, after the last measurements
samples was similar. By the eighth day after the milk
were made, the samples (which smelled very strongly
had been opened, all samples had developed a growth by then) were discarded.
on the surface, and smelled bad. For the seven days, The original cartons of milk were opened once at the
e 0 (x) at low frequencies (f < 5 GHz) decreased with
beginning of this series of tests, and then again a week
time, then began increasing as the milk began to sepa-
after being left in the refrigerator. There was no notice-
rate into two phases. The upper phase, in contact with
able deterioration of the refrigerated milk, and the
the probe, was more transparent (more like water), while
microwave spectra of the three refrigerated samples were
the lower phase was denser, both optically and physi-
indistinguishable from those made the week before.
cally. Separation of fat or oil was not specifically ob-
In addition to the above, spectra of one sample of
served. Presumably, the probe is more sensitive to the whole milk diluted successively with deionized distilled
upper (water-like) phase, so as the milk separates, its water were measured. These are shown in Fig. 4. Not
measured permittivity is expected to become more like
surprisingly, these spectra approach that of deionized
that of water. The low frequency end of the e00 (x) curves
distilled water as the milk becomes more dilute. The evo-
increase monotonically with time. This may be due to an
lution of the parameters of Eqs. (1) and (2), when fitted
increase in the concentration of ions (important in low
to these curves and compared with the same parameters
frequency microwave absorption, see Metaxas & Mere-
from fitting undiluted samples of low fat and skim milk,
dith, 1993) associated with the spoiling process. Two

Fig. 4. Plots of the permittivity of water and of whole milk diluted


Fig. 2. Replotting the data of Fig. 1b as a ratio with respect to their with deionized distilled water at relative concentrations of milk/
pure water counterparts, e0 ðxÞ=e0W ðxÞ and e00 ðxÞ=e00W ðxÞ. Designations solution by weight: (a) 1 (pure milk), (b) 1/2, (c) 1/4, (d) 1/8, and (e) 0
are the same as those used in Fig. 1. (pure water).
254 A.C. Nunes et al. / Journal of Food Engineering 76 (2006) 250–255

Table 2
Results of fitting Eqs. (1) and (2) to the real and imaginary parts of the permittivity spectra of various samples for frequencies between 1 and 20 GHz
Sample e 0 (x) data e00 (x) data
e0S e01 s (ps) (e0S  e01 ) s (ps) r (X1 m1)
Water 81.09 ± 0.16 6.70 ± 0.5 10.61 ± 0.09 75.63 ± 0.07 10.44 ± 0.04 0.036 ± 0.001
Whole milk 69.69 ± 0.17 10.49 ± 0.5 12.51 ± 0.09 62.82 ± 0.09 11.548 ± 0.04 0.666 ± 0.002
Low fat milk 72.42 ± 0.17 11.68 ± 0.5 12.74 ± 0.09 65.08 ± 0.1 11.60 ± 0.05 0.655 ± 0.002
Skim milk 74.30 ± 0.17 11.74 ± 0.9 12.68 ± 0.09 66.60 ± 0.1 11.62 ± 0.05 0.653 ± 0.002
Whole milk : solution (1:2) 75.75 ± 0.17 9.72 ± 0.9 11.70 ± 0.09 69.13 ± 0.09 11.062 ± 0.04 0.390 ± 0.001
Whole milk : solution (1:4) 78.68 ± 0.17 8.53 ± 0.5 11.26 ± 0.09 72.71 ± 0.08 10.82 ± 0.04 0.210 ± 0.001
Whole milk : solution (1:8) 79.99 ± 0.17 7.73 ± 0.5 10.975 ± 0.09 74.72 ± 0.08 10.65 ± 0.04 0.127 ± 0.001
The temperature of all samples was between 17 and 20 C.

gives insight into the sensitivity of these spectra to the


various different components of milk (see below).
The real part of the permittivity was fit by the Debye
relation (Eq. (1)), while the loss factor including ionic
conductance (Eq. (2)) was fit to the measured spectra
of the imaginary part of the permittivity. For water,
the resulting value of eS = 81.09 ± 0.16 from the fitted
Debye function is close to both theoretical and experi-
mental values given earlier (Ellison, Lamkaouchi, &
Moreau, 1996) The results are presented in Table 2.
These parameters are graphed in Figs. 5 and 6, against
the concentration of whole milk (1 = pure whole milk,
0 = pure water). The values for skim and low fat milk
are also plotted on these graphs at dilutions of the whole
milk corresponding to equal concentrations of fat (0.43
for low fat, and 0.083 for skim). Fig. 6. The three parameters (e0S  e01 , s, and r) of the imaginary part
Of these six parameters, e0S increases most signifi- of the permittivity (from least-squares fitting Eqs. (1) and (2) to the
spectra) of various dilutions of whole milk. The circles correspond to
cantly with a decrease in fat content. Since the largest the parameters obtained from undiluted skim, low fat, and whole milk.
contributor to e0S is the water, fat having much a smaller They are placed at the concentration (same values as in Fig. 4)
dipole moment, we believe that the presence of fat di- corresponding to the fat content of that of the appropriately diluted
whole milk.

lutes the waterÕs permittivity, so that as the fat content


is reduced and the water content increased accordingly,
so is the permittivity of the mixture. Decreasing the con-
centration of all components (diluting the milk) causes
changes in all parameters. e0S increases more rapidly with
dilution than with reduction of fat content, suggesting
that perhaps roughly half of the change in this parame-
ter reflects fat content. e01 , decreases more significantly
with dilution than with changes in fat content. This
may indicate that the permittivity of and hydrophilic
interactions of the milkÕs non-fat components (which
would lower the relaxation frequency of the sample—
see Ryynänen, 1995) may be as important as their dilu-
tion of the water dipole moment in affecting sample
Fig. 5. The three parameters (e0S , e01 , and s) of the real part of the permittivity. Since it is highly unlikely that free ions con-
Debye permittivity (from least-squares fit to the spectra) of various tribute to either e0S or e01 (both of which reflect energy
dilutions of whole milk (the same concentrations as in Fig. 4). The storage in the system rather than loss), it is sensible to
circles correspond to the parameters obtained from undiluted skim,
low fat, and whole milk. They are placed at the concentration
conclude that determining these two parameters alone
corresponding to the fat content of that of the appropriately diluted should be enough to permit an estimate of the relative
whole milk. fat, to carbohydrate and protein content of a sample.
A.C. Nunes et al. / Journal of Food Engineering 76 (2006) 250–255 255

The losses due to ionic conduction, as reflected by the the 191 used in this study, simplifying the instrumenta-
value of r, decrease with dilution, but not with reduc- tion required.
tion of fat alone. This behavior is as expected. Since
the low frequency end of the e00 (x) spectra of a given
sample, at which ionic losses are most important, in- Acknowledgements
creases monotonically with spoilage, it is likely that this
indicates an increase in the presence of ionic metabolic The authors wish to thank Joan-Manel Hernandez,
products, such as weak acids (sour) and bases (bitter). and Roger Amigó for technical help and advice.
Unfortunately, pH was not monitored in this study.
While these spectra were measured at 191 frequencies
at 0.1 GHz increments between 1 and 20 GHz, it was References
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