International Journal of Food Properties

ISSN: 1094-2912 (Print) 1532-2386 (Online) Journal homepage: https://www.tandfonline.com/loi/ljfp20

THE EFFECT OF POROSITY ON GLASS TRANSITION

MEASUREMENT

K. A. Ross , O. H. Campanella & M. R. Okos

To cite this article: K. A. Ross , O. H. Campanella & M. R. Okos (2002) THE EFFECT OF
POROSITY ON GLASS TRANSITION MEASUREMENT, International Journal of Food Properties,
5:3, 611-628

To link to this article: https://doi.org/10.1081/JFP-120015496

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©2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.

INTERNATIONAL JOURNAL OF FOOD PROPERTIES

Vol. 5, No. 3, pp. 611–628, 2002

THE EFFECT OF POROSITY ON GLASS

TRANSITION MEASUREMENT*

K. A. Ross, O. H. Campanella,{ and M. R. Okos

Department of Agricultural and Biological Engineering,

Purdue University, West Lafayette, IN 47907, USA

ABSTRACT

Texture is considered a key quality parameter determining the accept-

ability of many porous foods. Dynamic mechanical thermal analysis
(DMTA) is commonly employed in food and polymer science research as
a means of measuring the glass transition (Tg) of materials. In the field of
food science, Tg measurements have been used to characterize the tex-
tural changes of food materials. However the effect of sample porosity
and different sample preparation techniques on Tg measurement using a
DMTA have not been investigated. The objectives of this study were
to compare Tg measurements of identical materials varying only with
porosity and to examine the effect of sample preparation technique on
Tg measurements. Both starch based extrudates and synthetic polymers
with different porosities were tested with DMTA. For comparison,
representative samples from the porous specimens were obtained and
subjected to one of three methods of Tg determination: 1) ground into a
powder and compressed into tablets for testing with DMTA, 2) ground
into a powder and tested by differential scanning calorimetry (DSC), and
3) ground into a powder and tested by controlled strain rheometry.
Porosity was observed to affect the measurement of the glass transition
using DMTA. The extrudate samples containing the lowest porosity
exhibited a Tg range 22
C lower than the extrudate samples with the

*Purdue Research Paper #16590

{
Corresponding author. Fax: (765) 496-1115; E-mail: campa@ecn.purdue.edu

611

DOI: 10.1081=JFP-120015496 1094-2912 (Print); 1532-2386 (Online)

Copyright # 2002 by Marcel Dekker, Inc. www.dekker.com
612 ROSS, CAMPANELLA, AND OKOS

highest porosity. Also, the polymer samples with the lowest porosity
showed a Tg range 20
C lower than the polymer samples with the highest
porosity. The tablets (no pores) did not show any significant difference in
Tg as measured by DMTA nor did the ground samples (no pores) mea-
sured by DSC and controlled strain rheometry. This study shows that
porosity of the sample affects Tg measurement. Care should be taken
when reporting Tg values as porosity may introduce an artifact in Tg
measurements using DMTA.

INTRODUCTION

The importance of the glass transition of materials has long been

recognized in determining the behaviour of amorphous synthetic polymers
during processing and the concept of the glass transition has been adopted
for a better understanding on the behaviour of biopolymers during proces-
sing.[1] Measurements of glass transition have also received attention in the
food science literature and research has been performed with the aim of
relating the glass transition with textural quality.[2]
There are a wide variety of techniques that can be used to measure the
glass transition of materials and these include: differential scanning calori-
metry (DSC), dynamic mechanical thermal analysis (DMTA), thermal
mechanical analysis (TMA), and nuclear magnetic resonance (NMR).[3]
Interestingly, the study by Kalichevsky et al.[3] indicated that glass transition
temperature range measured depended upon the test method used. They
attributed this fact to each different test method being sensitive to different
degrees of molecular mobility which could be reasonably associated to the
glass transition (Kalichevsky et al.[3]). Therefore there are many methods
available to food science researchers that are capable of measuring the glass
transition range temperature and the measurement of the glass transition
depends on the method used.
Notably, DMTA is a very common test method used by food science
researchers to determine the glass transition temperature range of food
materials.[4] For example, Brent et al.[1] used DMTA to characterize the glass
transition of extruded cereal melts and Nichols et al.[5] used DMTA to
determine the glass transition of amorphous amylopectin sheets. The method
by which DMTA measures the glass transition applies a small sinusoidal
strain of known amplitude and thereby measures the resulting stress as a
function of temperature.[5] There are three mechanical properties that are
obtained with DMTA and these include storage modulus (E0 ), loss modulus
(E00 ) and tan d. The glass transition can be characterized by different mea-
sured parameters, e.g., a sharp drop in E0 , a peak in E00 or a peak in tan d.[5]
Therefore explicitly stated, the measurement of the change in mechanical
properties is paramount to determining glass transition of materials. With
POROSITY AND GLASS TRANSITION MEASUREMENT 613

respect to DMTA, it also follows that factors that affect the mechanical
properties of a material will also affect the measurement of the glass
transition.
Regarding the measurement of mechanical properties of foods, there is
much literature available concerned with characterizing the textural quality
of food with measurements of mechanical properties.[6711] Literature has
indicated that the mechanical properties of a material are the direct con-
sequences of the material microstructure and therefore they are affected by
these microstructural characteristics.[6,7] Moreover, researchers have noted
that the presence of pores and the degree of porosity affect the mechanical
properties of the food materials.[12714] Nicholls et al.[5] indicated that cellular
foam-like systems have been used to model crisp foods. They stated that
mechanical failure depends on the cellular structure and the material prop-
erties of the matrix. It was noted by Attenburrow et al.[15] that the structure
of many cereal based foods consists of a porous structure and they may be
described as food foams. It was stated that the key parameter used to
characterize microstructure in relation to mechanical properties is the ratio of
the bulk density of the foam to the density of the cell wall material.[15]
Furthermore, Attenburrow et al.[15] indicated the relationship between the
mechanical properties of porous cereal based foodstuffs and microstructure
may be understood in terms of theoretical treatments that have been devel-
oped by Gibson et al.[16] for a general class of cellular=porous materials.
Work has been performed on extruded foods in order to characterize their
mechanical properties.[12,17719] It has been shown that the mechanical
properties of extruded food products are influenced by moisture content,
density, and porosity.[11]
It follows that the justification of this research was motivated by the
realization that the DMTA measures the glass transition temperature range
via changes in mechanical properties. However, these mechanical properties
are affected by porosity. Therefore the specific objective of this research was
to examine the effect of porosity on the measurement of the glass transition
temperatures.

MATERIALS AND METHODS

Sample Preparation-Corn Based Cheese Curl Extrudates

Samples of corn based cheese curl extrudates (i.e., cheezies) were

obtained from a local grocery store (West Lafayette, IN) and cut into rec-
tangular test specimens. The average dimensions of the rectangular speci-
mens were 45  2.1 mm, 4  0.22 mm, and 2  0.1 mm for length, width and
thickness respectively. The dimensions of the specimens were measured with
a digital caliper (Mitsbushi, Japan).
614 ROSS, CAMPANELLA, AND OKOS

Representative samples of the rectangular test specimens were subjected

to one of five different relative humidity (RH) environments to alter the pore
size of the test specimens. The salts used were lithium chloride (LiCl),
potassium acetate (KAc), sodium chloride (NaCl), potassium chloride (KCl),
and potassium sulfate (K2SO4) (Sigma Chemicals, St. Louis, MO) and they
produced the following RH environments respectively, 11, 22, 75, 85, and
98% at 25
C. Also, representative samples of the pore modified rectangular
test specimens were ground into powder using a mortar and pestle. All of the
specimens (rectangular and powder) were dried in a vacuum oven (LabLine
Instruments Inc., Melrose Park, IL) for 24 h at 70
C.[20] This was done in
order to reduce the samples moisture content. Additionally, all of the vacuum
oven dried samples were equilibrated to the same moisture content (10.6%)
by subjecting to a LiCl environment (11% RH) at 25
C and testing was
performed on all samples after constant moisture content (10.6%) was
achieved. The common moisture content of 10.6% was determined by
obtaining representative samples of both the powder and the rectangular
specimens that had been equilibrated in the common LiCl RH environment
and analyzing for moisture content. The samples were collected and dried in
a convection oven (Blue M, Blue Island, IL) for 24 h at 120
C.[20] The mass of
the samples before and after drying was read on an electronic ( 0.01 g)
balance (Denver Instruments Co., Denver, CO). The average of three read-
ings was noted and moisture content was obtained on percent wet basis.
All of these steps were done to ensure that all of the pore modified
samples had approximately the same moisture content and therefore this
parameter was not considered a variable in the experiments. Also repre-
sentative samples from each initial pore modified rectangular specimen
containing 0.45 g of the ground ‘‘cheezie’’ powder were pressed into tablets
using a pneumatic press (Carver Inc., Wabash, IN) under 4500 psi of pres-
sure. After compression, the tablets were equilibrated again in the LiCl
environment for 24 h at 25
C prior to testing. This was performed to ensure
that the moisture content of the tablets did not change due to water
absorption=desorption from ambient during the formation of the tablet.

Sample Preparation Polymer

Polyethylene polymer samples with varying degrees of porosity were

obtained from the Porex Company (Georgia, AT). These samples came in
three classes which are presented in increasing degree of porosity: fine,
medium, and coarse with 15745, 45790, and 907125 mm pore size ranges,
respectively as specified by the company. It should be explicitly stated here
that the samples were identical in composition and varied only in porosity.
Samples were cut into rectangular test specimens. The average sample
dimensions for the rectangular specimens were 45  1.8 mm, 4.1  0.9 mm,
POROSITY AND GLASS TRANSITION MEASUREMENT 615

2.0  0.82 mm for length, width and thickness respectively. Representative

samples of the rectangular test specimens were ground into a powder.

Dynamic Mechanical Thermal Analysis (DMTA)

The rectangular ‘‘cheezie’’ test specimens, rectangular porous poly-

ethylene test specimens, and ‘‘cheezie’’ tablets were tested in dynamic thermal
mechanical analyser (DMTA) (Polymer Labs Mark I Dynamic Mechanical
Spectrophotometer, Shropshire, England). The parameters utilized during
testing were a temperature increase of 5
C=min, a temperature range of
57130
C, a frequency of 1 Hertz and a strain level of 4 mm which caused
deformations in the sample that had within the linear viscoelastic range. The
test geometry used was single cantilever.

Differential Scanning Calorimetry (DSC)

The ground cheezie and polymer powders were tested with a differential
scanning calorimeter operated on standard scanning mode (2920 Modulated
DSC, TA Instruments, New Castle, DE). The parameters used for differential
scanning calorimetry (DSC) were a temperature increase of 5
C=min and a
temperature range of 57140
C. The samples were analyzed in hermetically
sealed aluminum pans. The DSC was calibrated by measuring the melting
point of indium (157.44
C). An empty aluminum can was used as the
reference holder. The average weight of ground cheezie sample tested was
8.21  0.42 mg and the average weight of synthetic sample analyzed was
5.354  0.31 mg.

Controlled Strain Rheometry

A controlled strain rheometer (Viscotech, Lund, Sweden) was used. The

parameters for the controlled strain rheometry tests included a parallel plate
geometry, a temperature increase of 5.0
C=min with a temperature range of
57140
C for the synthetic polymer sample and a temperature range of
57100
C for the extrudate sample.[21] The amount of synthetic sample used
for testing was 0.22 g whereas the amount of extrudate sample was 0.20 g.

Apparent and Substance Density of Biological Extrudates

The apparent density (ra) of the cheezie was determined from the mass
(m) and the apparent volume (va). The mass of all of the specimens was
obtained after being equilibrated in the LiCl RH chamber. It was determined
616 ROSS, CAMPANELLA, AND OKOS

with an electronic balance,  0.01 g, (Denver Instruments Co., Denver, CO).

The mean apparent volume of the rectangular porous specimens was
obtained by measuring the length, width, and thickness of the specimens with
a digital caliper (Mitsbushi, Japan). The mean apparent volume was the
average of 3 determinations. The apparent density was obtained from the
following equation:
m
ra ¼ ð1Þ
na
Extrudate samples were crushed into powder and the substance volume
(vs) of the extrudate powder was determined by gas displacement, using a
helium stereo-pycnometer (SPY-2, Quatrochrome Corp., Syosset, NY). The
gas pycnometer was operated at an absolute pressure of 33.3 psi. The sub-
stance volume values reported are the average of 3 determinations. The
substance density was obtained from the following equation:
m
rs ¼ ð2Þ
ns
The apparent porosity (ea), defined as the fraction of air or void fraction
in the sample, was estimated from the equation:
ra
ea ¼ 1  ð3Þ
rs

RESULTS AND DISCUSSION

Polymer

The results of Tg range measured with the DMTA, DSC, and the rhe-
ometer for the porous polyethylene polymer are given in Table 1. It should be
stated that a synthetic polymer was chosen in order to reduce the effects of
biological variability and as a control for testing the effect of porosity of
measurement of the glass transition since it has been noted in the literature
that biological materials are highly variable and may yield high standard
deviations from experimental measurements.[22,23] It is acknowledged that the
glass transition of a heterogeneous material (as the extruded biological
material used in this research) can be expected to be broad and difficult to
measure.[24] In essence, it may be difficult to obtain meaningful glass tran-
sition measurements from multi-component materials. Additionally, physico-
chemical changes may occur due to the method used for altering the porosity
of the extruded biological material. Therefore, the use of a synthetic polymer
serves as a good control that enables to eliminate most of the problems
created by the sample preparation of biological materials.
POROSITY AND GLASS TRANSITION MEASUREMENT 617

Table 1. Glass Transition Measurements of Synthetic Polyethylene Polymer in Porous Form

by DMTA and Powder Form by DSC and Controlled Strain Rheometer (n ¼ 3)

DMTA DSC Rheometer

Synthetic Polymer Tp Tm0 Tm00
Sample (
C)  % COV

( C)  % COV

( C)  % COV

Coarse Polymer 104.9  3.4a 66.7  3.9a 59.80  3.9a

Medium Polymer 90.9  2.1b 61.6  3.3a 59.97  2.8a
Fine Polymer 83.3  2.8c 64.1  3.7a 60.73  1.9a

Tp means that Tg range was determined by tan delta peak.

Tm0 means that Tg range was determined by the midpoint heat capacity change.
Tm00 means that Tg range was determined by the midpoint of G0 values as a function of
temperature.
COV is the coefficient of variation.
Different letters within a column indicate significant differences (p ¼ 0.05).

An attempt was made to press the polymer samples that had been
ground to powder into tablets. This would have allowed for polymer speci-
mens with pores (porous rectangular specimens) and polymer specimens
without pores (tablets) to be tested with the same test (i.e., DMTA). The
polymer tablets did not maintain their integrity upon sample loading in the
DMTA. Therefore the only non-porous polymer specimens that could be
tested were in powder form and by using DSC and a controlled strain
rheometer.
There is a significant difference in Tg temperature range measured by the
DMTA. The largest average Tg value was 104.9
C for the coarse synthetic
polymer sample. The fine synthetic polymer sample had the smallest average
Tg value reported at 83.3
C. Statistical analysis (ANOVA) was performed on
the data and it determined that the values were significantly different at
p ¼ 0.05. The Tg range values (Tp) reported were taken as the tan delta peak
from the experimental DMTA graphs. Kalichevsky et al.[3] noted that in
synthetic polymers the tan d peak is commonly used as a convenient defini-
tion of the glass transition. Figure 1 shows a representative DMTA plot
containing both E0 and tan delta vs. temperature for the synthetic polymer.
The Tg range values obtained by DSC were taken from the observed
midpoint of the endothermic heat capacity change (T0 m) which is in accord
with the method used by Kalichevsky et al.[3] Figure 2 shows a representative
DSC scan. The DSC results were subjected to statistical analysis (ANOVA)
and it was determined that there is no significant difference (p ¼ 0.05) in Tg
measured by DSC when the polymer sample is tested in powder form and the
effect of porosity is eliminated.
Tg range values obtained by the controlled strain rheometer (T00 m) were
determined from the midpoint of the change in slope of the G0 values plotted
618 ROSS, CAMPANELLA, AND OKOS

Figure 1. Representative two peaks tan d vs. temperature plot obtained with DMTA.

Figure 2. Representative DSC scan.

POROSITY AND GLASS TRANSITION MEASUREMENT 619

against temperature. The method was the same as that outlined by Sterling
et al.[21] Again, statistical analysis (ANOVA) of the powder form of the
synthetic polymer showed no significant differences (p ¼ 0.05) in Tg as mea-
sured by controlled strain rheometry. Figure 3 shows a representative plot
containing values of storage modulus (G0 ) as a function of temperature.
However, it must be acknowledged that the fitting of the G0 vs. temperature
curve with the Fermi’s model as suggested by Peleg[25] was included in the
figure. Peleg[25] indicated that the change in mechanical properties in the Tg
range of many biological and some synthetic materials can be described by
the following equation:

G0 ðTs Þ
G0 ðTÞ ¼    ð4Þ
T  T 0c
1 þ exp
a0

where Ts is a reference temperature, taken as the temperature where the

material is in the glassy state, Tc0 is the inflection point of G0 (T) where
G0 (Tc0 ) ¼ G0 (Ts)=2, and a0 is a constant representing the steepness of the
G0 (T) curve in the transition region.[25]
The following Tc0 values were obtained by fitting the Fermi’s model to
the data for the synthetic polymers: coarse polymer, 64.7
C; medium poly-
mer, 52.4
C; and fine polymer, 78.3
C.
The Tc0 for the coarse and medium polymer are similar to those
obtained from the midpoint method of Sterling et al.[21] but the fine polymer

Figure 3. Representative G0 versus temperature plot obtained with controlled strain

rheometry.
620 ROSS, CAMPANELLA, AND OKOS

Tc0 values are nearly 20
C higher than the values obtained from the midpoint
method[21] which are given in Table 1. The reason for these differences may
be attributed to the shape of the G0 vs. temperature plots. Peleg[26] indicated
that Tc0 specifies the inflection point of the curve G0 versus temperature,
which may not coincide with the glass transition of the material. This
explains the difference in values obtained with the method of Sterling et al.[21]
and the inflection point as determined by the fitting model suggested by
Peleg[25] for the fine polymer. This further demonstrates the importance of
not only acknowledging the method of sample preparation, the test method,
and test conditions, but also the method of data analysis when discussing the
Tg range of materials.

Extrudates

Table 2 shows the apparent porosity and apparent density measure-

ments of the porous extruded specimens after they were subjected to various
relative humidity (RH) environments in order to alter their porosity. It was
thought that higher RH environments would be a factor that may cause the
sample to collapse, allowing the pores present to shrink and thereby decrease
the porosity of the specimens. Research performed by Krokida et al.[27] and
Fan et al.[28] support this idea, their works have shown that collapse and
shrinkage of freeze-dried food material and extruded melts are influenced by
the glass transition temperature. Krokida et al.[27] showed that when freeze-
dried food materials were subjected to a temperature above their glass
transition temperature, their structure was observed to collapse, their bulk
density increased, and porosity decreased. Fan et al.[28] found that shrinkage
and collapse of extruded melts ceased when the processing temperature was
below Tg þ 30
C. For completeness it must be stated that the glass transition
is not the only factor governing collapse and shrinkage and a full discussion
of this phenomena in foods during drying is given by Rahman.[29] Never-
theless it is known from literature that moisture content affects the glass

Table 2. Porosity and Apparent Density Measurements of Porous Extruded Samples (n ¼ 3)

Pore Modifying Porosity Apparent Density

RH (unitless)  % COV (g=cm3)  % COV

LiCl-11% 0.862  4.8a 0.053  3.9a

KAc-22% 0.839  3.8a 0.063  3.5b
NaCl-75% 0.818  5.4a 0.084  3.2c
KCl-85% 0.699  5.2a,b 0.105  3.1d
K2SO4-98% 0.355  4.2a,b,c 0.194  3.1e

COV is coefficient of variation.

Different letters within a column indicate significant differences (p ¼ 0.05).
POROSITY AND GLASS TRANSITION MEASUREMENT 621

transition temperature of biomaterials since moisture acts as a plasticizer that

reduces glass transition temperature and encourages structural collapse and
thereby reduces porosity.[27,30] Thus, it was hypothesized that samples held
over the highest RH environments should have shown the highest apparent
density and the lowest porosity. This is what is shown in Table 2. However,
it is noted that there is only a slight difference in the porosity measurements
between the intermediate RH environments, notably in the 22775%
RH range. Nevertheless, there are significant differences, as determined by
ANOVA (p ¼ 0.05) in porosity measurements between the samples condi-
tioned in LiCl and KCl; LiCl and K2SO4; KAc and KCl; and KAc and
K2SO4 environments. This fact will be further discussed in relation to Tg
measurements of the extrudates given in Table 3.
In DMTA measurements, two peaks were observed when porous
extrudates were tested. However only for the second peak or main transi-
tion peak there appeared to be a correlation between porosity and Tg.
Before discussing the presence of the two peaks, the relationship between
porosity and Tg of the second peak will be discussed. Table 3 shows the
value of the two peaks observed in the tan delta data obtained for the
porous extrudates. Figure 4 shows a representative DMTA plot for
the extrudate samples illustrating the two peaks. For the first peak or low
temperature transition peak, there appeared to be no correlation between
porosity and the temperature at which the peak occurs. However, the
temperature associated with the second peak or the main transition peak

Table 3. Glass Transition Measurements of the Extruded Samples in Porous Form and
Tablet Form by DMTA and Powder Form by DSC and Controlled Strain Rheometer (n ¼ 3)

Porous Specimen
DMTA Tp Tablet
Pore (
C)  % COV Specimen Powder DSC Powder Rheometer
Modifying DMTA Tp Tm0 Tm00
RH Peak 1 Peak 2 (
C)  % COV (
C)  % COV (
C)  % COV

LiCl-11% 46.1  8.9a 89.3  8.3a 17.8  12.9a 26.42  12.9a 37.9  16.3a
KAc-22% 44.5  9.9a 85.1  7.4a 17.1  13.4a 31.24  13.8a 33.5  15.8a
NaCl-75% 41.7  9.8a 82.5  7.4a 16.4  10.4a 30.86  12.6a 34.2  16.9a
KCl-85% 44.4  7.4a 75.6  5.2a,b 15.5  5.8a 33.58  10.4a 38.2  12.6a
K2SO4-98% 42.4  8.5a 66.9  6.6a,b,c 17.9  10.6a 29.59  8.1a 33.5  13.1a

Tp means that Tg range was determined by tan delta peak.

Tm0 means that Tg range was determined by the midpoint heat capacity change.
Tm00 means that Tg range was determined by the midpoint of G0 values as a function of
temperature.
COV is coefficient of variation.
Different letters within a column indicate significant differences (p ¼ 0.05).
622 ROSS, CAMPANELLA, AND OKOS

Figure 4. Representative DMTA plots including both tan d and E0 versus temperature
curves.

appeared to change with an increase in the RH of the environment and a

corresponding decrease in porosity. This is due to the fact that for the
samples showing a statistically significant difference in porosity (e.g., LiCl
and K2SO4) there is also a statistically significant difference in Tg. Con-
versely, for the samples in which the difference in porosity was not statis-
tically significantly different there was no statistically significant difference
in Tg. These results seem to indicate that there is a correlation between
porosity and Tg measurements.
As previously mentioned two peaks were observed in the DMTA data
generated for the porous extrudates. Work performed by Kalichevsky et al.[3]
also observed two peaks in their study using DMTA to examine the Tg of
amorphous amylopectin. The first peak they observed was near 50
C which is
in nearly the same temperature as the first peak temperatures obtained in this
study. Kalichevsky et al.[3] indicated the origin of the first peak or low
temperature transitions was uncertain however, they hypothesized that its
presence may be due to short range chain motions or a lipid melting tran-
sition. It should be stated that the ratio of the height of the first tan d peak to
the second tan d peak obtained in these experiments was greater than the
ratio of the first tan d peak to the second tan d peak obtained by Kalichevsky
et al.[3] This fact may be explained by indicating that the tan d peak relates
quantitatively to the volume fraction of the relaxing phase and therefore if
the first peak was due to lipid melting, the extrudates in this experiment
simply had more lipid present than the amorphous amylopectin in the
experiment of Kalichevsky et al.[3] This may be a plausible explanation since
POROSITY AND GLASS TRANSITION MEASUREMENT 623

Kalichevsky et al.[3] indicated that amylopectin contains relatively little lipid

and vegetable oil was listed as a major ingredient of the extrudate utilized in
this experiment. Interestingly, Kalichevsky et al.[3] also stated that low tem-
perature transitions were detectable by DSC experiments. However, it was
noted that the low temperature transitions measured with DSC were not
dependent on moisture content while the higher temperature transitions were.
This helps to corroborate the idea that the low temperature transitions may
be associated with the presence of lipid.
As mentioned, extrudates that had porosity modified were ground down
and subjected to either testing with DSC in powder form, testing with con-
trolled strain rheometry in powder form, or were pressed into tablets and
tested with DMTA. The aim of all of these tests was to measure the Tg of the
specimens without the presence=effect of porosity. It was deemed beneficial
to test the specimens that had been pressed into tablets with DMTA because
this allowed for the effect of porosity to be investigated using the same test
equipment as the porous specimens. It can be seen in Table 3 that the results
for the powder tested with DSC, powder tested with controlled strain rheo-
metry, and the tablets tested with DMTA show that there is no significant
difference, as determined by ANOVA (p ¼ 0.05), between samples when the
effect of porosity was eliminated. It is noted that there is a difference in the
values obtained for the same specimens between test methods however this
was somewhat expected on the basis of the findings of Kalichevsky et al.[3]
However there was only one transition associated with the tablets tested with
DMTA, and powder tested by DSC and controlled strain rheometry. At first
thought this appears to be inconsistent with the results showing two peaks for
the porous extrudate samples measured with DMTA and the work by
Kalichevsky et al.[3] These findings may be due to the fact that the samples
were ground with a mortar and pestle made of porcelain and it is possible
that a majority of the oil=lipid in the native porous sample was released upon
grinding or crushing and absorbed by the porcelain.
The Tg range values obtained by the controlled strain rheometer for the
extrudate samples in powder form were determined from the midpoint of the
G0 versus temperature curves (Tm00 ) which was the same procedure outlined
by Sterling et al.[21] It was also the same method used for the synthetic
samples in this study. Table 3 shows the results obtained by the controlled
strain rheometer for the extrudate powder samples. Statistical analysis
(ANOVA) of the extrudate powder samples showed no significant differences
(p ¼ 0.05) in Tg between samples conditioned in the different RH environ-
ments. The rheometer data obtained for the extrudate powder samples was
analyzed with the Fermi’s model. The inflection points T0 c obtained by fitting
the Fermi’s model to the data for the extrudate powder samples were: 78.3
C
LiCl, 50.3
C; KAc, 54.1
C; NaCl, 53.9
C; KCl, 53.7
C; and K2SO4, 57.9
C.
The values obtained by the Fermi’s model for the extrudate powder
samples are all nearly 20
C lower than the Tg range values (given in Table 3)
624 ROSS, CAMPANELLA, AND OKOS

obtained for the extrudate powder samples by using the midpoint method of
Sterling et al.[21] Again the reason for these results may be due to the shape of
the G0 versus temperature plots.
For completeness, the final moisture content of the samples that were to
be tested was examined to ensure that moisture content was within experi-
mental error as it has been stated that moisture content affects the Tg.[2,30]
As can be seen in Table 4 none of the specimens tested had statistically
significantly different moisture contents. Also, the moisture loss from the
sample during testing was examined. It was observed that there was a slight
loss of moisture by the samples with different porosity during testing with
DMTA, however there was no significant difference, as determined with
ANOVA (p ¼ 0.05), in the amount of moisture loss among the sample of
different porosity levels. Based on these results, it can be stated that the
different Tg values measured was not due to differences in moisture contents
or differences in moisture losses among the samples. For the synthetic
polyethylene samples, the final moisture content and moisture loss from the
samples during testing was not investigated by virtue of the nature of the
specimens.

Hypotheses

Results of this research show that it is most likely that the effect of
porosity on the measurement of the Tg is an artifact of the DMTA test. One
plausible explanation for samples with greater porosity levels exhibiting
higher Tg measurements may be due to the fact that porosity is inversely
related to thermal conductivity. Marousis and Saravacos[31] stated that
thermal conductivity increases linearly with bulk density. Since thermal
conductivity decreases with decreasing bulk density, samples with higher

Table 4. Average Final Moisture Contents and Average Moisture Loss by the Extrudate
Samples During Testing (n ¼ 3)

Pore Modifying Final Moisture Content DMTA Moisture Loss

RH (%)  SD (%)  SD

LiCl-11% 10.3  2.1a 9.1  1.5a

KAc-22% 9.9  1.9a 8.2  1.4a
NaCl-75% 10.9  2.0a 9.3  1.7a
KCl-85% 11.1  2.1a 9.9  1.7a
K2SO4-98% 10.8  1.9a 7.0  1.6a

SD is standard deviation.
Different letters within a column indicate significant differences (p ¼ 0.05).
POROSITY AND GLASS TRANSITION MEASUREMENT 625

porosity will take a longer time to reach the desired temperature resulting
in higher detected glass transition temperatures. Results of Tanaka and
Tanaka,[32] who measured the Tg temperature range of epoxy resin compo-
sites with silica microballoons, support the above explanation. Tanaka and
Tanaka[32] indicated that the Tg of the composites was high when the resin
and the filler were mixed prior to the addition of curing agent and thereby
had a large amount of gas incorporated into the composite. However, the Tg
of the composites was lower when the resin and the curing agent were mixed
prior to the addition of the filler and this allowed for the amount of gas
incorporated into the composite to be lessened. It was also noted that the Tg
decreased with further degassing of the composites. A way to investigate the
extent of the effect of decreased bulk density (i.e., less gas=air present) on
thermal conductivity would be to run the DMTA test at a very slow heating
rate to allow the temperature of the sample to reach its equilibrium value.
However, a problem with this solution would be that a very slow heating rate
would allow for moisture loss from the sample and this would incorporate a
different artifact in glass transition measurements.
Also, the DMTA applies a constant oscillatory strain to the sample
being tested whereas the temperature increases.[4] This constant oscillatory
strain supplies kinetic energy to the test material and therefore frictional
forces arise. Presumably, more frictional forces arise in the sample with lower
porosity due to the closer proximity of the solid structure on a macroscopic
level. The increased frictional forces present in the less porous material may
serve as an additional energy source to the thermal energy being supplied to
the test material during the DMTA test. Thus, there is more energy asso-
ciated with the less porous samples than the more porous sample at the same
temperature. This may be an artifact and contribute to the less porous
material exhibiting a lower Tg temperature range. This explanation may be
strengthened by the fact that Weipert[33] acknowledged that the presence of
friction in DMTA tests should be investigated and if necessary should be
quantified.
Alternatively, the effect of pore size may be a real result. Phase transi-
tions of organic materials confined in controlled pore glasses have been
studied and a relationship between pore size and phase transitions has been
identified. Mansare et al.[34] studied the phase transitions of 4-methoxy-
benzilidene-40 -n-butylaniline in controlled porous solids and found that as
the pore size decreased the primary phase transition of melting temperature
and the secondary phase transition of Tg were both observed to decrease.
Jackson and McKenna[35] noted that crystalline melting, superfluid and solid-
solid phase transitions shift to lower temperatures for materials confined to
small pores. It has been shown by Jackson and McKenna[36] that for ortho-
terphenyl and benzyl alcohol glasses formed in pores, there was a reduction
in the primary transition of melting temperature as pore size decreased. They
ascribed the decrease in Tg with a decrease in pores size to the large surface to
626 ROSS, CAMPANELLA, AND OKOS

volume ratio of the material adsorbed in the capillary. Although melting

behaviour is a primary phase transition and Tg is a secondary phase transi-
tion phenomenon a similar reasoning of preferential adsorption of water in
smaller pores, which can be likened to capillaries, may account for the
lowered Tg observed in the samples with smaller pores. Furthermore work
done by Jackson and McKenna[36] on ortho-terphenyl and benzyl alcohol
glasses formed in pores indicated that there was a reduction in Tg as pore size
decreased. Although, the work cited was concerned with measuring the phase
transitions of a material confined in pores, they show that geometry can
affect the measurement of the phase transitions and there is an effect of pore
size on apparent material properties.

CONCLUSIONS

In all, it has been shown that the quality of porous foods is dictated by
texture and the measurement of Tg has been noted in the literature to be a
viable method of obtaining an index of texture and therefore an index of
quality. DMTA is commonly used in food science research and is a preferred
method of obtaining Tg values. This study shows that for both synthetic
porous specimens and biological porous specimens, the level of porosity
affects the measurement of the Tg. Most likely the effect of porosity on
measuring the Tg is an artifact of the DMTA test. Therefore, the effect of
porosity should be acknowledged when discussing Tg measurements and
future work should be performed to elucidate the actual cause of the
observed effect of porosity.

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Received September 4, 2001

Accepted December 23, 2001