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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
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
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.
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
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