Effect of Freeze-drying Conditions on Shrinkage and

Porosity of Dehydrated Agricultural Products

M. K. Krokida, V. T. Karathanos 8: Z. B. Maroulis”’

Department of Chemical Engineering. National Technical University ot Athens.
Zografou Campus. 157X0 Athens, Grccct

NOMENCLATURE

111 Mass (kg)

N Number of experimental points
P Number of estimated parameters
C’ Volume (I)
&S Sum of squares
T Temperature (K)
G’ Elastic (storage) modulus (Pa)

“To whom correspondence should bc addressed. E-mail: maroutis(~~;orfcas.chemeng.ntua.gr

xi0
370 M. K. Krokida et al.

G” Viscous (loss) modulus (Pa)

n” Complex viscosity (eqn (9)) (Pa s)

Greek

Porosity ( - )
Density (kg I - ‘)
Dynamic testing frequency (s- ’ or rad s-‘)

Subscripts

Air
% Bulk
P Particle
S Dry solids

INTRODUCTION

The quality of dehydrated products is characterized by the appearance, colour,

texture, taste, retention of nutrients, porosity and other physical properties, such as
density and specific volume. This quality depends on the drying method and drying
conditions (Krokida & Maroulis, 1997; Krokida et al., 1997). Freeze-dried foods are
characterized by high-quality characteristics such as low bulk density, high porosity,
superior taste and aroma retention, and better rehydration properties compared to
products of alternative drying processes: air, vacuum, microwave and osmotic drying.
Freeze-drying is a two-step dehydration process, in which the product is first
frozen and then the water is removed by sublimation. Frozen products are two-
phase mixtures of ice needles and concentrated amorphous solution (CAS) (Bellows
& King, 1972; Watanabe et al., 1991), in which the solvent is the unfrozen water.
The unfrozen water may be of the order of 30% of the weight in the CAS and it
may vary with the temperature. The final product quality depends on whether or not
the frozen product was kept below a critical temperature, the collapse temperature,
during the sublimation of ice.
The collapse temperature is related to the glass transition temperature (T’,) of
the maximally frozen concentrated solute (Pikal et al., 1988; Pikal & Shah, 1990)
and it represents the temperature above which the solute matrix loses its shape
(Levine & Slade, 1988) and quality decreases. The glass transition temperature may
be determined by differential scanning calorimetry (DSC) or by mechanical spec-
trometry. The value obtained for T’, for several plant tissues including potato, apple
and sweet potato as well as osmotically dehydrated potato was -45°C (Anglea et al.,
1993). The similarity in the glass transition temperature for these fruits as well as for
some osmotically treated potato samples allowed us to assume that the T’, for plant
materials is close to -45°C. The collapse temperature during freeze-drying has been
related to the collapse temperature of the CAS. Increased plasticization of the CAS
by unfrozen water occurs above the melt temperature of ice, decreasing the viscosity
and causing acceleration of shrinkage during freeze-drying.
Ferry (1980) proposed that above 7’g the amorphous matrix viscosity decreases
steeply with temperature. Williams et al. (1955) proposed a relationship relating
viscosity to the temperature difference above Tg, which can be applied from 7, to
r, + 100. The viscosity changes significantly with temperature, for temperatures
above Ts.
During freeze-drying, the ice sublimation creates pores, the walls of which may
shrink due to surface forces or gravity. High viscosity of the CAS may prevent or
retard shrinkage. Thus it seems very interesting to investigate the effect of viscosity
on the porosity of the freeze-dried products.
Bellows & King (1972, 1973) have proposed physical relationships predicting that
shrinkage occurs when the viscosity of the CAS is in the range of 10” to 10’ Pa s.
Karathanos ef al. (199ha,b) investigated the structural collapse (porosity and pore
size distribution) of fresh and osmotically dehydrated potato, apple and celery
during freeze-drying. Three different temperatures were used: below. near and
above the glass transition temperature (rl, = -45°C).
The objective of this investigation was to determine the effect of freeze-drying
conditions (pressure or temperature) on the collapse of the structure of freczc-dried
apple, banana, potato and carrot. Freeze-drying was performed under controlled
drying conditions regulating pressure during drying. Simple equations have been
used to express the effect of temperature on product structural properties of freeze-
dried materials, such as bulk density and porosity. The complex viscosity of frozen
materials has also been related to temperature and its role on the final product
porosity has been examined.

MATHEMATICAL MODELLING

Assuming dried material to consist of dry solids and air, the following definitions
can be considered:
v,=v,+v;, (1)
where V,, V, and Vi, are the total volume and the volumes of dry solids and air
pores, respectively (m’).
The bulk (or apparent) density ijI,, and the particle (or solid) density I),,, of the
dried material (kg I ~ ‘) are defined:

where m, is mass of dry solids (kg).

The porosity i: is defined as the ratio of air pores volume Vi, divided by the total
volume of the product V,:

V;,
(:= -

V,
Combining eqns (l)-(4), the porosity (>z)can be calculated:
372 M. K. Krokida et al.

i.=1_!!2 (5)
PPS

The effect of the drying method and drying conditions on the particle density of
dried material was investigated through two recent papers (Krokida & Maroulis,
1997; Krokida et al., 1997). Through these investigations it is clear that the particle
density of dried material is not dependent on temperature, but it is dependent only
on the material. On the other hand, bulk density is dependent on temperature, but
this effect has not yet been established theoretically. In order to examine the
influence of temperature on these properties, bulk density could be considered as a
temperature function, using the following equation:

IJI,~= mxp@T) (6)

where a, h are parameters dependent on the material, and T is the initial sample
temperature (K).
The influence of temperature on porosity is extracted from eqns (4) and (6):

c = 1- --!- exp(bT) (7)

I’ps

The influence of temperature on the complex viscosity n* of fresh materials could

be predicted through a linear equation:
~*=c+dT (8)
where c, d are constants (Pa s) and (Pa s K-‘).
The complex viscosity (nY’) (Pa s) of the (viscoelastic) material can be expressed
as:

,1* =
\ (G’)’ + K-w
(I)
(9)

where 01 is the dynamic testing frequency (Hz or rad s-l), G’ and G” are the storage
and elastic moduli in N m -’ (A n gl ea et al., 1993) and they are measures respectively
of the elastic and viscous behaviour of the (viscoelastic) structure.
Combination of eqn (7) and eqn (8) gives the influence of complex viscosity on
porosity:

6: = I - L exp(h(n* - c)ld) (10)

Pps

During sublimation the pressure above the sample can be assumed to be the vapour
pressure of ice (Weast, 1986). The vapour pressure data were correlated to the
sample temperature using an exponential equation:
P=(3 x IO-“)exp(O.l04T) (11)
where P is the pressure (bar) and T the temperature (K).
 The values of the constants a, h can be determined by fitting the proposed eqn (6)
to the experimental data. This can be done by minimizing the following residual sum
of squares:

(13)

where j&s and /I*,,\ are the experimental and the predicted values of bulk density, N
is the number of exoerimental Doints and D is the number of estimated uarameters.
The parameters ‘c and d (if linear ein (8) can be determined Ly fitting the
proposed equation to the experimental data, minimizing the following residual sum
of squares:

whcrc II”, /z*,,,, are the experimental and predicted values of complex viscosity.

MATERIALS AND METHODS

Measurement of bulk density, particle density and porosity

Fresh bananas, apples, carrots and potatoes were used as test materials. Carrots and
potatoes were steam-blanched for 3 min and then immersed along with bananas and
apples in 2% sodium bisulphite solution for 5 min (Van Arsdel & Copley, 1964).
Freeze-dried materials were cut into cylinders of approximately 20 mm diameter
and 8 mm height. They were frozen at -35°C for 48 h, tempered for 1 h in liquid
NJ, and freeze-dried for 24 h using a Lyovac Gt 2 laboratory freeze-dryer. Freeze-
drying was performed under various vacuum conditions, ranging from 0.04 to 3 mbal
to obtain initial sample temperatures below, near and above the glass transition
temperature of the tissues (T’, = -45°C (Anglea et NI., 1993). The vacuum was
reduced by leaking air through one of the pressure release valves. The temperature
of the sample was measured in the centre of the sample during freeze-drying using
a thermocouple.
After freeze-drying, the final weight, the total volume and the particle volume
were measured. Three replicates for each sample and method were measured. The
standard deviation was good, _+3%. The weight was measured by a Mettler AE-160
electronic balance with an accuracy of + lo- ‘g. The particle volume was measured
by a Quantacrome stereopycnometer (model SPY-j, Nyosset, New York) with an
accuracy of +O.OOl ml. The total volume of the samples was measured by immers-
ing them in n-heptane and by determining the volume displacement.
In order to estimate a mean representative value for the density of the clry solids,
I’,>53all dried samples of the same material were ground together and screened
through a 65 mesh sieve, and the weight and particle volume of the dry solids were
measured.
For the evaluation of the experimental data, the following method was adopted:
the particle density was estimated from eqn (3) and it was taken as a constant,
374 M. K. Krokida et al.

characteristic of the material. The bulk density (& and the porosity (E) were
estimated from eqns (2) and (5), respectively.

Measurement of viscoelastic properties

The complex viscosity of apple and potato were estimated by measurement of the
mechanical properties of the materials, G’ (storage modulus) and G” (loss mod-
ulus). The above properties of the products were estimated using a mechanical
spectrometer (RMS-800 by Rheometrics, Piscataway, New Jersey, USA) (Anglea et
al., 1993). The complex viscosity ~1”was estimated by the above mechanical proper-
ties, G’ and G”, and applying eqn (9).

RESULTS AND DISCUSSION

Equations (6) and (8) were fitted to the experimental data and the results of
parameter estimation are summarized in Table 1. The corresponding values of dry
solid density and of residual sums of squares are also given in Table 1.
A comparison between experimental (points) and calculated values (solid lines) is
shown in Figs l-3.

Bulk density

The bulk density of freeze-dried plant materials, as determined experimentally, was

strongly affected by the freeze drying conditions (Fig. 1). More specifically, all
materials did not shrink significantly during freeze-drying at low temperatures
(lower than the estimated glass transition temperature T’, = -45°C) and they
resulted in low bulk densities. The shrinkage was considerably more significant when
the freeze-drying occurred at reduced vacuums and, consequently, at higher tem-
peratures. The fitting of exponential relation (6) to the experimental data of bulk
density is considered satisfactory. The bulk density of freeze-dried materials
decreased as the temperature was increased from -50 to -8°C. The bulk density of
apple showed the greatest dependence on temperature, the density of carrot
followed, while banana and potato showed the lowest dependence. Among the fresh
samples, apple has the lowest bulk density, which is due to its greater contained
volume of air. Therefore, during sublimation of the ice crystals, an additional
volume (the empty pores) is available to shrinkage above the shrinkage temperature.

TABLE I
Results of Parameter Estimation

Materiul I’p5 h c sp, sn*

(kg I-‘) (kg 1 ‘) (K?,) (Pa s) (Pa s K~ ‘) (kg:- ‘) (Pa s)

Apple 1.65 1.1 x 10 h 0.048 - 1.0 x lo’* 3.0 x lOI 0.050 0.017
Potato 1.60 0.003 0.018 -0.6 x 10” 2.0 x lOI 0.036 0.025
Carrot I .75 0.00 1 0.020 0.020
Banana 190 0.027 0.010 0.040
 Effct of freeze-drying corlditiom 37.5

Porosity

The porosity of freeze-dried materials is shown in Fig. 2. The porosity was greatly
affected by the freeze-drying conditions. At low temperatures, the porosity for all
materials was the highest noticed (90%) while it decreased for drying at higher
temperatures. The reduction of the porosity varied from 30% for apple to 10% for
the other materials. During freeze-drying, detrimental effects occurred due to the
glass to rubber transition of the CAS and the melting of ice which plasticized the
matrix and decreased the porosity, as the initial sample temperature was increased.
Fresh apple has the greatest porosity value, which means that the pore percentage
is higher and therefore a greater volume of pores is available to shrink. Moreover.

OS

0,4
t

f 0,3

z!
0
I
a’
2
s 012
m t

0,1

0 +
220 230 240 250 260 270

Temperature (K)

Fig. 1. Bulk density versus temperature of freeze-dried materials and fitting of eqn (6).
376 M. K. Krokida et al.

the composition of the materials tested and the complex viscosity of each sample
may be factors which control the extent of shrinkage during freeze-drying for several
materials.

Complex viscosity

The complex viscosity of frozen material seems to be greatly affected by tempera-

ture (Fig. 3). More specifically, it decreases linearly as the temperature increases
above the glass transition temperature (T’, = -45°C). During freeze-drying at tem-
peratures above Yg, the complex viscosity of the structure decreased, causing
acceleration of the shrinkage. The higher the temperature, the more intense this
phenomenon. The structural collapse that occurred during freeze-drying was due to

Expertiental
A Apple
0 Potato
l Carrot
m Banana
~Cakxlated

0.7 I

220 230 240 250 260 270

Temperature (K)

Fig. 2. Porosity versus temperature of freeze-dried materials and fitting of eqn (7).
 Efkt of’fkae-dr?/irlg condi~iom 377

the viscosity reduction, caused by the increased ‘plasticity’ of the solid matrix which
surrounds the water ice crystals. This phenomenon is more intense for apple than
for potato and therefore the complex viscosity decreases more sharply for apple
than for potato.

Relationship of structure collapse and viscoelastic properties of the solid matrix

The viscoelastic properties (C’ and G”) of fresh and frozen potato and apple
showed a broad maximum of the G” versus temperature curve and a simultaneous
steep drop of G’ at the same temperature region of about -45°C (Anglea rt cl/.,
1993). This has been related to the glass transition phenomenon of the concentrated
amorphous solution by several researchers (Levine & Slade, 1988; Cocero Rr Kokini,

I___ --+~_-_--__~_ -~
_b___ (

230 240 250 260 270

Temperature (K)

Fig. 3. Complex viscosity versus temperature for frozen apple and potato
378 M. K. Krokida et al.

1991). At temperatures above -35°C both viscoelastic parameters (G’ and G”)
decreased significantly and, as a result, the complex viscosity (n*, eqn (9)) was
sharply reduced as well.
The reduction of the viscoelastic properties, which takes place at temperatures
above the glass transition temperature of the concentrated amorphous phase (T’J
may be an explanation for the significant collapse of the structure of materials
subjected to freeze-drying above the Trg, as suggested by Pikal and Shah (1990)
Liapis et al. (1996) and Karathanos et al. (1996a). The complex viscosity of the
matrix may be an indication of the final porosity and other structural properties.
This is shown in Fig. 4, in which the porosity of freeze dried apple and potato is
related to the complex viscosity of frozen materials. Porosity decreased as the
complex viscosity was decreased for both materials. Figure 4 shows a remarkable
coincidence of the curves of final porosity versus complex viscosity. The rheological
properties of apple are similar to those of potato, with the exception that there is a
sharper drop of viscosity of apple than potato as the temperature was increased. The
lower complex viscosity of apple compared to that of potato at temperatures above
T’, may be the reason for the higher tendency to collapse of apple than potato at
higher temperatures (or equivalently at conditions of reduced vacuum). The lower
complex viscosity of apple than potato may be related to the higher sugar content of
apple. The sugars have been responsible for a dramatic drop of the mechanical
properties as proved by Anglea et al. (1993).
As the frozen ice crystal is sublimated in a freeze-drying process the concentrated
amorphous solution tends to collapse. It is assumed that the collapse occurs due to
the surface tension of the capillaries. The opposite force, which tends to keep the
matrix non-collapsed is due to the high complex viscosity of the matrix. Therefore,
at relatively high temperatures the collapse phenomenon occurs at a short time,
while at low temperatures the collapse phenomenon is very slow due to the much
higher complex viscosity. If collapse does not happen in a short time, then it would
never happen, because as the water is evaporated from the sample, the structure
looses its ‘flexibility’ and becomes too stiff and difficult to collapse.
From the data given above, it becomes obvious that there is a direct relationship
between the rheological changes (due to the temperature) and the porosity decrease
(or bulk density increase). The relationship seems to be linear although a more
drastic effect of temperature on both structural collapse and porosity was expected.
The effect of temperature on the complex viscosity, as predicted by application of
the WLF equation (after Williams et al., 1955) (see Ferry, 1980; Simatos et al., 1989;
Roos & Karel, 1991). In this research, however, instead of the drastic reduction of
complex viscosity (n*) with temperature (as predicted by the WLF equation), an
almost linear effect of Ton II* was found (Fig. 3). The deviation from the expected
viscoelasticity nature and the WLF equation is attributed to the complexity of the
structure of plant materials. An Arrhenius, rather than a WLF, dependence of some
T’,-dependent degradation mechanisms has been observed by Liapis et al. (1996).

CONCLUSION

The physical properties of freeze-dried materials depend on temperature during

freeze-drying. For all materials, collapse occurred above the glass transition tem-
perature and the phenomenon becomes more intense as the temperature increases,
controlling the bulk density and porosity of the dried materials. The reduction of
complex viscosity, as the temperature of the frozen materials increased, caused a
structural collapse and therefore a reduction of the final porosity. The bulk density
was related to temperature through an exponential relation, so the bulk density and.
therefore, the quality of the final product can be easily controlled by selecting the
appropriate vacuum and consequently controlling the initial sample temperature.

Experinental

A Apple
0 Potato
1.0
-Calculated 1

0.9

0.8

0.7 L TV
---i
0 I 2 3 4 5
Complex Viscosity (MPa s)

Fig. 4. Porosity versus complex viscosity for frozen apple and potato
380 M. K. Krokidu et al.

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