Sjoqvist 2010

Processing and Water
Absorption Behavior of Foamed

Potato Starch
MIA SJÖQVIST, ANTAL BOLDIZAR* AND MIKAEL RIGDAHL

Department of Materials and Manufacturing Technology
Chalmers University of Technology, SE-412 96 Göteborg, Sweden
ABSTRACT: Starch foams were prepared from four types of potato starch
using two-step extrusion with an intermediate conditioning step at 53% relative
humidity in order to control the moisture content. The moisture content was the
driving force for the expansion during the second extrusion. The second
extrusion was performed with two different dies in order to achieve differences
in porosity of the materials. Glycerol in combination with water was used as
plasticizer for the starches. The rheological properties of the melts and the
moisture content of the starch materials prior to the expansion were determined.
The porosity of the expanded structures was characterized using environmental
scanning electron microscopy imaging and density measurements. The absorp-
tion capability of the starch-based foams was investigated using aqueous NaCl
solutions, and the water uptake of thin starch-based films from humid air was
also evaluated. Foams prepared from amylopectin potato starch were found to
exhibit the highest porosity, the lowest density, and the greatest absorption
capability, both from water and from humid air. Not only the density but also the
absorption capability was influenced by the porosity level.
KEY WORDS: potato starch, foam, extrusion, water absorption.
INTRODUCTION
T here is an emerging interest in finding renewable raw materials

for biodegradable plastic products, especially for packaging pur-
poses and for other products with a short lifetime. About 40% of all
*Author to whom correspondence should be addressed.

E-mail: antal.boldizar@chalmers.se
JOURNAL OF CELLULAR PLASTICS Volume 46 — November 2010 497

0021-955X/10/06 0497–21 $10.00/0 DOI: 10.1177/0021955X10377802
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498 M. SJÖQVIST ET AL.
plastics are used as packaging materials. Starch is a biopolymer that

meets the requirements for both renewability and degradability and it is
thus a promising candidate for such products. Starch is abundant in
most parts of the world and is relatively cheap. It is possible to convert
starch into a thermoplastic material by disrupting its native semi-
crystalline structure [1]. Disruption of the structure, that is, gelatiniza-
tion of the starch, is commonly achieved by heating in the presence
of water.
Specimens in the form of films and foams have been prepared from
many types of starches, and also by combining starch with synthetic
polymers or other biopolymers [2–8]. Starch-based foams have been
prepared by processes such as extrusion, freeze-drying, baking in a hot
mold, and microwave treatment [9–12]. One challenge often encoun-
tered when working with biopolymers, such as starch, is their water
sensitivity [13].
Starch is composed mainly of the two polysaccharides, amylose, and
amylopectin. Both amylopectin and amylose have an a(1!4) linked
D-glucan backbone. Amylose is essentially linear and amylopectin is
extensively (1!6) branched. Amylose has a molecular mass of 105–106 g/
mole and amylopectin 2 107 to 5 108 g/mole [14–16]. Depending on
their botanical origin, starch materials vary in composition, such as
the amylose/amylopectin ratio and the degree and type of crystallinity,
and this affects both their properties and their processability. Potato
starch has been shown to exhibit the highest swelling ability among the
different types of starches due to its higher content of phosphate groups
[17]. The phosphate groups repel one another and thereby weaken
the bonds between chains and permit a higher hydration level [18].
This swelling capacity has been reported to be mainly a property of
amylopectin [19].
The hydroxyl groups of the glucose units account for the water
sensitivity of starch.
These hydroxyl groups yield a high hygroscopicity and the starch
material rapidly adapts its moisture content to the surrounding humi-
dity. As a result, its physical properties also change rather dramatically
with changes in the moisture content [20]. Water is a strong plasticizer
for starch and also for many other biopolymers; and a higher water
content leads to a decrease in the glass transition temperature, Tg, of
the material. The importance of the glass transition and the influence of
water on the properties of starch materials have been stressed by Slade
and Levine [13,21]. There are also other plasticizers for starch which can
be combined with water. The most common appears to be glycerol which
gives a more permanent plasticizing effect than water, that is, it does not

Processing and Water Absorption Behavior of Foamed Potato Starch 499
evaporate as readily. It may be noted that starch/glycerol systems have

been reported to absorb more water than pure starch [22].
For foaming of starch, water in the form of steam can be used as a
blowing agent. In the extrusion process, the water pressure builds up
with increasing temperature in the extruder, and the pressure drop as
the material passes through the die causes an expansion of the material
due to the release of steam [23]. After expansion, the cells formed can
either be stabilized or allowed to collapse. If the temperature of the
material decreases below Tg stabilization is favored. If the temperature
of the foamed starch remains above Tg the risk of cell collapse is greater.
A high moisture content after the expansion is thus expected to lead to a
larger number of collapsed cells. For cereal starches, Kokini and
co-workers [24] reported a relationship between Tg and the foaming
capacity; the greatest expansion being achieved in a temperature range
from Tg to 1008 above Tg [24]. A large expansion ratio in connection with
extrusion is generally favored by a large pressure drop. The pressure
drop depends on the material, but it can be increased by increasing the
screw rotational speed. Here the shape of the die is also of importance.
Foaming gives structural materials with a reduced weight. In
addition, the lower density of the porous structure provides other
functionalities such as improved insulation and, in the present case, a
greater absorption capability. If the water sensitivity of starch materials
could be controlled, porous starch would be of potential interest for
absorption products such as diapers. The scope of this study has been to
assess and characterize the foaming ability, the porous structure, and
the water absorption behavior of four different types of potato starch
foams. The porosity of the foams has been varied and the processing
conditions during the extrusion foaming closely monitored.
MATERIAL AND METHODS
Materials
Four types of potato starch in granular form were supplied by Lyckeby

Stärkelsen, Sweden; native potato starch (NPS), hydroxypropylated and
oxidized potato starch (HO-NPS), oxidized potato starch (O-NPS), and
amylopectin potato starch (PAP). The HO-NPS had an average number
of carboxylic groups per anhydroglycose unit of 0.04 and its degree of
substitution was 0.11 [25]. The degree of substitution of the O-NPS was
0.03 [25]. The PAP material was developed by Lyckeby Stärkelsen and
Svalöf Weibull using genetic engineering in order to suppress the

synthesis of amylose [26]. Glycerol (recapture) from Prolabo, Sweden,

was used as plastizicer, 3 parts by weight of glycerol being added to
10 parts of starch.
Compounding
Starch and glycerol were mixed by hand and then fed into a Buss
compounding extruder type Buss PR 46, Switzerland, diameter D ¼
46 mm and length L ¼ 11D. The purpose of this extrusion was to achieve
both gelatinization of starch and mixing of starch and glycerol. The
screw rotational speed was 24 rpm and the barrel and the die
temperatures were set to 908C. A circular die with a diameter of
2.5 mm was used. The extrudate was granulated with a Univex take-off
unit from Brabender OHG, Duisburg, Germany.
Conditioning
Samples containing glycerol were conditioned in a closed chamber

with a saturated salt solution of Mg(NO3)2, giving a surrounding relative
humidity (RH) of 53% at 238C [27], for a minimum of three days prior to
any measurements or processing. The water content of the samples was
determined gravimetrically, using a Mettler Toledo AG285 analytic
balance after drying in a vacuum oven at 1108C for 5 h. Measurements
were made in triplicate.
Melt Properties
A Rheoscope 1000 CEAST 6742/000(Ceast SpA, Pianezza, Italy)

capillary viscometer was used to determine the melt properties of the
conditioned materials at 1208C. The shear viscosity was measured as a
function of the shear rate. Three different capillaries were used, all with
a diameter of 1 mm but with different length-to-diameter ratios (L/D): 5,
10, and 40, respectively. Corrections according to Rabinowitz and Bagley
were applied. The results were fitted to a power-law equation between
the shear stress() and the shear rate ():
_
¼ K _ n ð1Þ
The parameters K (consistency constant) and n (flow index) were

evaluated from the dependence of the shear viscosity ( ¼ =)
_ on the
shear rate.

The viscometer was also equipped with a rotating disc unit situated
below the exit of the capillary. The capillary had a diameter of 1 mm and
a length of 10 mm. Initially the disc had the same tangential velocity as
the extruded strand, 15 mm/s, and the velocity was then increased at a
rate of 0.63 mm/s2; the strand was extended and both the melt strength
as well as the elongation at break were recorded.
Expansion of the Material
The conditioned pellets were fed into a Brabender compact extruder,

Brabender OHG Duisburg, Germany. The diameter of the screw was
D ¼ 19 mm and length L ¼ 25D. The extruder had three individually
controlled temperature zones, set to 958C, 1208C, and 1408C. Two
different dies with temperature control were used; a circular die with a
diameter of 2 mm and a length of 20 mm and a slit die with a width of
100 mm, land length 140 mm, and height 1.5 mm. The temperature at
the die was set to 1608C and the screw rotational speed was kept at
150 rpm. The pressure in the extruder before the die was measured, and
the pressure drop over the die was thus calculated.
Environmental Scanning Electron Microscopy
The structures of the foams extruded from the two different dies
were investigated with environmental scanning electron microscopy
(ESEM). Samples were cut with a scalpel. ESEM images were obtained
with a Philips XL 30 ESEM operated at 12 kV. Images were taken at
50 magnification at 0.9 Torr.
Water Absorption
Samples with weights of 0.3–0.5 g were placed in bags of polyester net.

The bags were sealed and immersed in 0.9% NaCl aqueous solutions for
1, 5, 30, and 60 min, and weighed after each immersion. The samples
were allowed to drain for 2 min before the weighing. After the 60 min
immersion, the samples were centrifuged for 2 min at 1500 rpm. The
weight of the absorbed liquid was evaluated as:
A ¼ ðw2 w1 Þ=w1 ð2Þ
where A is the absorbed weight per gram of starch, w2 is the weight of
sample after immersion and w1 is the weight of the sample prior to
immersion.

Film Preparation
Starch films were prepared from aqueous starch solutions at a

concentration of 3 wt%. Starch was dissolved in deionized water while
heated, to achieve gelatinization. Four different solutions were used;
NPS/H2O, NPS/H2O/glycerol, PAP/H2O, and PAP/H2O/glycerol. The
glycerol content was 3 parts of glycerol per 10 parts of starch by weight.
The solutions were spin-coated onto QSX 301 gold QCM-D sensors at
2000 and 4000 rpm.
Thickness Measurements
A quartz crystal microbalance with dissipation monitoring, QCM-D

E4Õ , Q-sense AB, Göteborg, Sweden, together with a QHM 401 humidity
module, was used in order to measure the weight increase of thin spin-
coated starch films after exposure to the surrounding relative humidity.
The thickness of films was calculated from the measured weight change
using the software Q-toolsÕ , Q-sense AB.
The spin-coated films were placed in an axial flow chamber, which
allows simultaneous measurement of both frequency and dissipation
changes, enabling measurement of weight changes in very thin layers
[28,29]. From the weight change, the change in thickness of the film can be
calculated. In the humidity module, the chamber containing the QCM-D
sensor, was separated from the liquid by a Gore TexÕ membrane. The
relative humidity at 238C was controlled by five different saturated salt
solutions; LiCl (11%), MgCl2 (33%), Mg(NO3)2 (53%), NaCl (75%), K2SO4
(97%), and pure milliQ H2O (100%). Salt solutions were pumped through
the module with an Ismatec peristaltic pump at a speed of 0.2 mL/min.
With this equipment, the changes in resonance frequency and dissipation
could be monitored in real time. Each measurement started with LiCl,
that is, at the lowest relative humidity of 11%. The relative humidity was
increased stepwise to 100%. After 100% was reached, the films were again
exposed to the lowest RH environment 11%.
Density
The density of the porous starches was measured by a volumetric

displacement method, two displacements media being used. Samples
were weighed on a Mettler Toledo AG285 analytic balance, and the
volume was measured by placing the samples in granular potato starch

and water, and measuring the increase in volume of the displacement

medium. Similar methods have been used by Segnini [30] and
Bhatnagar and Hanna [31]. Mean values were obtained by averaging
five replicates of each material. Finally, the density was calculated by
mass divided by displaced volume.
RESULTS AND DISCUSSION
Moisture Content after Conditioning
The moisture contents of the materials after conditioning at 53% RH,

are listed in Table 1.
PAP had the highest moisture content, 13.0%, in agreement with
previous findings [32], and HO-NPS contained the lowest amount of
moisture. As already noted, glycerol is known to enhance the hygro-
scopity of starch, and a glycerol/starch system is thus expected to absorb
more water than a pure starch system [22].
Melt Properties of Glycerol-containing Starches
Figure 1 shows the melt viscosities of the glycerol-plasticized

materials at 1208C as a function of the shear rate. Melt viscosities of
pure materials were not within the measurable region. HO-NPS had a
significantly lower melt viscosity than the other materials. The melt
viscosities of PAP, NPS, and O-NPS were within the same range. The
hydroxypropylation leads to a decreased molecular weight for HO-NPS
compared to PAP and NPS [33]. The lower viscosity of HO-NPS could be
due to a lower molecular weight. In Table 2, the power law indices n are
listed and HO-NPS had the highest n-value, indicating that it exhibited
Table 1. Moisture content and melt properties of starch melts. Standard deviation
within parenthesis.
Moisture content Elongation at break Melt strength

Material (%) (%) (mN)
NPS 11.4 148 (4) 250 (21)
PAP 13.0 189 (8) 140 (18)
O-NPS 12.2 197 (7) 160 (23)
HO-NPS 11.3 347 (12) 140 (20)

105
HO-NPS
PAP
NPS
O-NPS
104
Viscosity (Pa s)
103
102
100 101 102 103 104
Shear rate (1/s)
Figure 1. Viscosity vs shear rate for HO-NPS, O-NPS, PAP, and NPS at 1208C.
Table 2. Power law parameters n and K of starch

melts at 1208C.
Material n K(Pa sn)

NPS 0.33 85,910
PAP 0.39 52,450
O-NPS 0.26 109,410
HO-NPS 0.51 11,260
a more Newtownian behavior than the other materials. O-NPS had the
lowest n-value and thus displayed the strongest shear-thinning
behavior. The melt strength and the elongation at break at 1208C are
listed in Table 1. NPS had the highest melt strength of the four
materials, whereas the melt strengths of HO-NPS, PAP, and O-NPS
were all very similar. The elongation at break was significantly higher in
the case of HO-NPS, 350%, and NPS exhibited the lowest value, 150%.
The PAP and O-NPS melts exhibited a similar elongation at break which
was somewhat higher than that of NPS.

Table 3. Densities and thicknesses of foamed materials and processing

parameters.
Density Thickness Mass flow Pressure drop

(kg/dm3) (mm) (g/s) (bar/mm)
Material Circular die Slit die Circular die Slit die Slit die Circular die Slit die
NPS 0.95 0.98 4.2 2 0.019 0.79 1.1 0.16
PAP 0.35 0.73 7.2 1.3 0.023 0.94 0.54 0.08
O-NPS 0.65 0.86 4.3 1.5 0.021 0.85 0.84 0.12
HO-NPS 0.54 0.82 5.2 0.7 0.037 1.5 0.73 0.10
Processing Behavior of the Starch Materials
All the materials were expanded at the highest screw rotational speed
of the extruder, 150 rpm, for both the dies used. The mass flow and
the pressure drop over the circular die were recorded and are given in
Table 3. HO-NPS exhibited the highest mass flow, which is to some
extent in agreement with its lower viscosity, and lowest NPS. The
highest pressure drop over the circular die was observed with NPS, and
the pressure drop was about 50% lower with PAP, see Table 3. The
HO-NPS material showed a large expansion ratio directly after the die,
particularly with the circular die, but the cells created, collapsed before
solidification. The other materials did not display similar collapse
behavior. Thermoplastic starch solidifies as its temperature decreases
below its glass transition temperature, Tg and the cell structure is then
fixed (immobilized). It is likely that the lower melt viscosity of HO-NPS
at temperatures higher than Tg, see Figure 1, compared to the other
materials allows for a more pronounced collapse of the cell structure
before solidification and before the temperature decreased below Tg.
Densities of the Foamed Materials
NPS had the highest density, 0.95 and 0.98 kg/dm3, regardless of
which die was used, whereas PAP displayed the lowest density in case of
foams prepared with both the slit die and the circular die, see Table 3.
The difference between the foams from the two dies was in general quite
large; foams prepared from the circular die had the lowest density and
the highest porosity. A comparison of the processing conditions and the
density of the foams reveal that a high porosity can be associated with a
low pressure drop. A corresponding conclusion is however not straight-
forward since different starch melts were used. The observation merely
illustrates the fact that the rheological properties (in shear and

elongation) and their temperature dependence are of substantial

importance with regard to the final density of the foams.
ESEM
Figures 2–5 show ESEM images of four materials prepared with two
different dies. In Figure 2(a) and (b), micrographs of NPS-based
materials produced with the circular die and the slit die, respectively,
are shown. NPS yielded a rather compact structure as shown in
(a)
(b)
Figure 2. ESEM image of foamed NPS produced from: (a) the circular die and (b) the
slit die.

Figure 2(a) (circular die), with some large pores present. In the case of
the slit die, Figure 2(b), the material is mostly solid.
The circular die yielded an O-NPS material with both large pores and
solid material present (Figure 3(a)). Looking into the pores there was an
indication of pores being interconnected and judging from the shape of
the cell walls there was also a tendency for the cells to merge. The slit die
(Figure 3(b)) also yielded a porous O-NPS material but a comparison of
the Figure 3(a) and (b) reveals that the pores were somewhat smaller
(a)
(b)
Figure 3. ESEM image of foamed O-NPS produced from: (a) the circular die and (b) the
slit die.

(a)
(b)
Figure 4. ESEM image of foamed HO-NPS produced from: (a) the circular die and (b) the
slit die.
when the slit die was used, and the amount of solid material seemed
to be higher.
HO-NPS, shown in Figure 4(a) and (b), yielded partly porous struc-
tures but with the circular die the cells appeared to have collapsed to a
great extent. The low viscosity of HO-NPS could be a reason for the
collapse. The pores in the foam prepared with the slit die were smaller
than those obtained when the circular die was used.
Figure 5(a) and (b) shows the porous structure of PAP, which
exhibited the highest porosity, especially with the circular die. Pores of

(a)
(b)
Figure 5. ESEM image of foamed PAP produced from: (a) the circular die and (b) the
slit die.
different sizes were present and almost no solid material was visible.
In all the materials, the circular die produced foams of higher porosity
and larger pores.
It is not easy to identify any clear relation between the porosity (or
density) of the foamed starches and the rheological properties as
evaluated here. A high deformation resistance as indicated by the melt
strength and a lower elongation at break combined with a relatively high
shear viscosity does not however appear to be favorable. Intuitively, this
would apply to the growth phase of the cells. With regard to the stability

of the cell structure preventing collapse, a low elongation at break would

appear to be a disadvantage. A low viscosity might also lead to a
collapsed structure, since a certain degree of stability can be attained
before the driving force for expansion ceases. This may have been the
case with HO-NPS. Furthermore, the nucleation of the cells must be
considered. The nucleating mechanisms may differ for the different
starch systems considered here.
Liquid Absorption Capacity of the Foams
In Figures 6–9 the absorption behavior of the foams produced with the
two different dies are compared pair-wise. The absorption medium was
2.5
Absorbed amount (g/g)
2
Circular die
1.5
Slit die
1
0.5
0
0.5 1 5 30 60 Centrifuge
Immersion time (min)
Figure 6. Absorption behavior of foamed NPS.
5
3 Circular die
2 Slit die
0
Figure 7. Absorption behavior of foamed PAP.

0.9% NaCl aqueous solution. For clarity, it should be pointed out that
the absorption test used here cannot distinguish between pore absor-
ption and absorption by the starch-based material itself. Both processes
occur simultaneously and probably also at a high rate (see the following
section on swelling of starch films.)
Figure 6 shows the water absorption behavior of NPS. The material
extruded through the slit die absorbed less at all times than that
extruded through the circular die. The porosity was low for NPS but it
was somewhat higher for material from the circular die, which may be a
reason for its higher absorptivity. The absorbed amount was quite
constant for immersion times from 30 s to 5 min, but at the longer
immersion times, 30 and 60 min, it increased. Since NPS yielded a rather
solid material, with hardly any pores, it is probable that the time
required to completely soak the sample was quite long. The increase in
4
3
Circular die
2
Slit die
1
0
Figure 8. Absorption behavior of foamed O-NPS.
5
3 Circular die
2 Slit die
0
Figure 9. Absorption of foamed HO-NPS.

absorbed amount with increasing time might thus be related more to

absorption by the starch material itself.
The amount of absorbed water in PAP, Figure 7, was larger in foams
prepared with the circular die than in those prepared with the slit die
which again might be associated with the difference in porosity. The
absorbed amount increased from 30 s to 1 min immersion time, but after
5 min immersion a decrease was noted. This decrease may be due to
dissolution of starch. After 60 min, a small increase can be noted in
the case of the material prepared with the circular die. PAP from the
circular die exhibited the highest absorption capability of all samples
after 1 min – 3.6 g absorbed water per gram of starch, which may to some
extent be attributed to its higher porosity.
The absorption behavior of O-NPS, Figure 8, was quite steady and
only small differences in the absorbed amount can be seen. The greatest
increase in water content was observed when the immersion time was
increased from 30 to 60 min. There was little or no difference in absor-
ption behavior in the foams from the different dies.
In the case of the HO-NPS, Figure 9, the difference in amount absorbed
by the foams from the two dies was quite large at the shortest immersion
time – 30 s, but at the longest immersion time 60 min, it was the same,
regardless of which die was used. The foam prepared from the circular die
exhibited the highest absorbed amount at 30 s but the amount decreased
when immersion time was increased to 1 min. Increasing the immersion
time further had little effect on absorbed amount.
All the samples were centrifuged after 60 min immersion, and all of
them lost a substantial amount of liquid due to this treatment. The
remaining absorbed amount was about the same for all samples, and there
was little or no difference between foams prepared with different dies.
Some trends in the absorption behavior can be noted. Foams prepared
with the circular die absorbed more, especially during short immersion
times. For HO-NPS and PAP, a decrease in the absorbed amount at
extended immersion times was observed, possibly due to dissolution of
the starch. An increase in the absorbed amount was evident at longer
immersion times in the samples with a low porosity. Although there
were some indications of a higher absorption capacity at higher porosity
levels in the case of these foams, the water-starch interactions as well as
the absorption characteristics of the material as such may also play a
role. Water may not interact with the different starch materials in the
same manner, and this may affect the absorption behavior (cf. also the
following section). The possible dissolution of starch is one example of
this. The absorption behavior may also be affected by the glycerol
distribution which can differ between the starch foams. A change in

porosity or pore structure will obviously also change the area of the
starch material exposed to water which in turn will affect the water
sorption capability.
The Effect of Relative Humidity on Starch Films
The thicknesses of the NPS, NPS/glycerol, PAP, and PAP/glycerol

spin-coated films in different relative humidities are shown in Table 4.
The initial thickness of the films, at 11% relative humidity was between
70 and 109 nm for films spin-coated at 2000 rpm. Films spin-coated at
4000 rpm were initially thinner, 47–64 nm. PAP films containing
glycerol were somewhat thicker than those without.
The trend for all the films was that the thickness increased with
increasing RH up to 97% RH; at higher RH levels the swelling was
dramatic. At 100% RH, equilibrium was never really reached. After the
films had been exposed to 100% RH for 5 min, the relative humidity was
again reduced to 11%. The change in thickness was then very rapid; within
10 s of exposure to 11% RH, the films regained their initial lower thickness.
The glycerol-containing films did not, however, regain their initial
thickness completely, suggesting that water was trapped within the film.
Figure 10 shows the degree of swelling of the PAP and NPS films at
different relative humidities. Films based on PAP swelled to a greater
extent than the NPS films at all RH levels. This is in agreement with
other observations [10] and with the higher absorption capability of the
PAP foams described in the previous section; that is, the absorption
Table 4. Thickness of starch, starch/glycerol, amylopectin; and amylopectin/

glycerol films spin-coated at 2000 and 4000 rpm at RH levels increased from 11%
to 100%, and then returned to 11%. Standard deviation within parenthesis.
Thickness (nm)
NPS/H2O NPS/H2O/Glycerol PAP/H2O PAP/H2O/Glycerol
Relative 2000 4000 2000 4000 2000 4000 2000 4000
humidity (%) rpm rpm rpm rpm rpm rpm rpm rpm
11 103 (2) 64 104 (5) 64 71 (1) 47 95 56
33 113 (3) 72 111 (6) 71 79 (1) 52 107 64
53 114 (3) 73 115 (6) 72 80 (1) 52 110 64
75 114 (3) 73 113 (6) 72 80 (1) 53 110 65
97 167 (7) 109 199 (11) 118 134 (2) 87 217 111
100 345 (45) 290 515 (45) 580 705 (15) 205 690 450
11 103 (2) 64 118 (2) 64 73 (1) 46 156 58

120
100
80 NPS
Swelling %
NPS/Glycerol
60
PAP
40 PAP/Glycerol
20
0
0 25 50 75 100
RH%
Figure 10. The swelling (in the thickness direction) of the spin-coated films when
increasing the relative humidity (RH).
behavior of the foam was also affected by the absorption characteristics

of the material as such and not by the porosity of the extrudates. The
difference in the degree of swelling between the PAP and NPS films
was most pronounced at the highest relative humidities, see Figure 10,
which approach the condition during the absorption test. NPS films
containing glycerol swelled more at the higher relative humidities, 97%
and 100%, than those without glycerol. At lower humidity levels,
33–75%, the NPS films containing glycerol swelled less than those
without. Similar behavior has previously been reported by Godbillot
et al. and Sala et al. [22,34] suggesting that the plasticizer occupied the
bonding sites on the starch, and that it was not until the surrounding
relative humidity exceeded 75% that the water uptake could increase
and exceed that of non-plasticized starch. PAP plasticized with glycerol
behaved somewhat differently. This film swelled more than the pure
PAP film at all RH levels. The large and quick swelling at 97% RH and
higher humidities and the rapid deswelling when the RH was reduced
indicated that water taken up at these high humidities was very loosely
bonded in the structure.
CONCLUSIONS
All the materials could be extruded at the highest possible screw

rotational speed of the extruder, regardless of which die was used.

The screw rotational speed is one important factor affecting the pressure
in the die of the extruder – higher the screw rotational speed higher the
pressure drop over the die. Thus the material blends were probably
expanded to the maximum extent under the available processing
conditions and with the equipment used. Foams prepared with the
circular die had a higher porosity for all materials, possibly due to a
larger pressure drop over this die. PAP foams displayed the lowest
density in foams prepared with both the circular and the slit dies. One
contributing reason for the higher expansion of PAP foams could be its
higher moisture content at the time of foaming. HO-NPS exhibited a
large expansion when extruded through the circular die, but the cells
collapsed to a large extent. The lower viscosity of HO-NPS could be a
reason for this behavior. Foams from the circular die generally displayed
a higher initial liquid absorption, probably because the higher pore
content permitted a faster transport of fluid into the material. PAP was
the material with the highest absorption capability, probably due to the
higher porosity of the material as well as the absorption characteristics
of the material as such.
ACKNOWLEDGMENTS
SCA Hygiene Products and the Knowledge foundation, through

the MARCHAL company graduate school at Chalmers University of
Technology, are acknowledged for the financial support of this study.
Dr Shabira Abbas of SCA Hygiene Products is acknowledged for
valuable discussions. Q-sense AB, Lyckeby Stärkelsen, and Lantmännen
AB are thanked for the experimental assistance and the supply of
materials. Dr J. Anthony Bristow is thanked for the linguistic revision of
the article.
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Processing and Water

Absorption Behavior of Foamed

MIA SJÖQVIST, ANTAL BOLDIZAR* AND MIKAEL RIGDAHL

KEY WORDS: potato starch, foam, extrusion, water absorption.

T here is an emerging interest in finding renewable raw materials

*Author to whom correspondence should be addressed.

JOURNAL OF CELLULAR PLASTICS Volume 46 — November 2010 497

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plastics are used as packaging materials. Starch is a biopolymer that

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evaporate as readily. It may be noted that starch/glycerol systems have

MATERIAL AND METHODS

Four types of potato starch in granular form were supplied by Lyckeby

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synthesis of amylose [26]. Glycerol (recapture) from Prolabo, Sweden,

Samples containing glycerol were conditioned in a closed chamber

A Rheoscope 1000 CEAST 6742/000(Ceast SpA, Pianezza, Italy)

The parameters K (consistency constant) and n (flow index) were

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Expansion of the Material

The conditioned pellets were fed into a Brabender compact extruder,

Environmental Scanning Electron Microscopy

Samples with weights of 0.3–0.5 g were placed in bags of polyester net.

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Starch films were prepared from aqueous starch solutions at a

A quartz crystal microbalance with dissipation monitoring, QCM-D

The density of the porous starches was measured by a volumetric

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and water, and measuring the increase in volume of the displacement

RESULTS AND DISCUSSION

Moisture Content after Conditioning

The moisture contents of the materials after conditioning at 53% RH,

Melt Properties of Glycerol-containing Starches

Figure 1 shows the melt viscosities of the glycerol-plasticized

Moisture content Elongation at break Melt strength

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Table 2. Power law parameters n and K of starch

Material n K(Pa sn)

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Table 3. Densities and thicknesses of foamed materials and processing

Density Thickness Mass flow Pressure drop

Processing Behavior of the Starch Materials

Densities of the Foamed Materials

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elongation) and their temperature dependence are of substantial

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of the cell structure preventing collapse, a low elongation at break would

Liquid Absorption Capacity of the Foams

Figure 6. Absorption behavior of foamed NPS.

Figure 7. Absorption behavior of foamed PAP.

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Figure 8. Absorption behavior of foamed O-NPS.

Figure 9. Absorption of foamed HO-NPS.

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absorbed amount with increasing time might thus be related more to

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The Effect of Relative Humidity on Starch Films

The thicknesses of the NPS, NPS/glycerol, PAP, and PAP/glycerol

Table 4. Thickness of starch, starch/glycerol, amylopectin; and amylopectin/

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behavior of the foam was also affected by the absorption characteristics