REGULAR CONTRIBUTED ARTICLES
B. Shi*, G. Wideman, J. H. Wang
Corporate Research and Engineering, Kimberly-Clark Corporation, Neenah, WI, USA
Improving the Processability of Water-soluble
Films Based on Filled Thermoplastic Polyvinyl
Alcohol
International Polymer Processing downloaded from www.hanser-elibrary.com by Kungliga Tekniska on August 14, 2015
Melt extrusion of polyvinyl alcohol (PVOH) is desirable over
commonly practiced solution film casting due to reduced en-
ergy input, environmental footprint, and processing cost, how-
ever, melt extrusion processing of plasticized polyvinyl alcohol
(PVOH) presents a significant processing challenge due to in-
herent adhension issues of extruded PVOH film to the surface
of equipment. This paper reports a method using inorganic fil-
lers such as CaCO3 and talc to facilitate the plasticized PVOH
processing for blown films.
Parameters are also identified for additional process studies
For personal use only.
to optimize the mechanical properties of blown films. It was
found that the preferred inorganic filler is CaCO3 for the
PVOH stickiness reduction. The filled PVOH films were found
to have delayed or reduced water solubility. It takes about 7
to 10 minutes for the filled PVOH films to dissolve in water
whereas the neat PVOH films are soluble in water instantly.
The delayed water solubility may be desirable for certain spe-
cialty applications such as packaging of pesticides during ship-
ping and storage. With improved processability by incorporat-
ing filler, the melt extrusion produced PVOH film should cost
less than the solution-cast PVOH films.
1 Introduction
Water soluble polymers such as polyvinyl alcohol (PVOH) are
one of the important commodity polymers for a variety of in-
dustries. For example, they are used in adhesives, thermal-sen-
sitive papers, gas barrier coating, building materials, packaging
films, polymerization, and textile sizing (Deboer and Yahl,
1985; Sewell, 2004; Herman, 2007). Kuraray, DuPont, and
Celanese are the major manufacturers of PVOH resins. Within
the area of film applications, polyvinyl alcohol is processed
through a solution casting method by companies such as
Monosol in Merrillville, IN, USA, or Aicello in Toyohashi, Ja-
pan. However, the solution process has a high processing cost
due to the energy required to evaporate large amount of water
* Mail address: Bo Shi, Corporate Research and Engineering,
Kimberly-Clark Corporation, 2100 Winchester Road, Neenah,
WI 54956, USA
E-mail: bshi@kcc.com
Intern. Polymer Processing XXVII (2012) 2
Carl Hanser Verlag, Munich
(up to 90 % of solution), this leads to high environmental foot-
print based on LCA (Life Cycle Assessment) considerations.
The process is also slow and inefficient. These factors resulted
in high cost of the PVOH films produced by this method. Due
to high cost, the applications of water-soluble PVOH films are
quite limited to high margin, low volume products. Therefore,
there is an unmet need to develop an alternative highly effi-
cient, low-cost and environmentally low footprint process for
making water-soluble PVOH films via melt extrusion.
There are numerous challenges to extrude PVOH via a melt
process. A direct extrusion of PVOH powder without plastici-
zation causes discoloration when it is heated near its melting
point about 200 8C. Therefore, PVOH is normally considered
as non-thermoplastic (Hodgkinson and Taylor, 2000).
In order to resolve the issue related to the direct melt extru-
sion, A. Schulman plasticized PVOH using proprietary formu-
lations and made it available in a pellet form (Aqua-sol 116)
for melt extrusion processing of neat films or blends (Wang
and Funk, 2009). Whitchurch and Cooper (2006) reported
advances in polyvinyl alcohol formulating and processing
technology that have enabled a family of water-soluble, biode-
gradable PVOH-based thermoplastic materials such as film,
sheet, fiber, foam, tubing, and molded article to be produced
without undergoing thermal or shear degradation. US Pa-
tent 7279510 to Stevens (2007) described melt extrusion of
PVOH-containing composition, which can be manufactured
on conventional extrusion equipment. The compositions in-
clude a lubricant such as a fatty acid amide, inorganic filler,
glycerin, and zinc stearate. In some cases, sorbitol or mannitol,
etc. has been used as well to thermoplastically process PVOH
in EP 0635545 to Famili et al. (1995). However, it has been
found that melt extrusion of PVOH becomes very unstable
and significant residues adhere to the surface of the extrusion
apparatus, requiring very careful control of processing condi-
tions, specialized extrusion equipment and frequent shut down
of the extrusion process and purging of the equipment (Wang
et al., 2000). In addition, the use of sorbitol results in plastici-
zer migration such as white spots on the film surface during
aging, reducing the PVOH appealing to the potential users
(Meisel and Wang, 2007).
A few examples of blends comprising PVOH and plant poly-
saccharides such as pectin or starch were documented by Mao
et al. (2000), Ke and Sun (2003), Fishman et al. (2006), and
231
 B. Shi et al.: Improving the Processability of Water-soluble Films
Dean et al. (2008), respectively. Glycerin was used as a plasti-
cizer for producing these blends. In addition, reactive extrusion
of polyvinyl alcohol and starches was carried out using ammo-
nium persulfate as an initiator and reported by Willett and Fin-
kenstadt (2006). With the presence of starch, material sticki-
ness was greatly reduced during processing of biodegradable
and water-sensitive films in comparison to the plasticized
PVOH alone (Wang and Shi, 2008). The recent approach is to
create bio-nanocomposites using PVOH, starch, clay and plas-
ticizers for packaging film applications (Alavi and Tang,
2009; Majdzadeh-Ardakani and Nazar, 2010).
The PVOH polymer has been reported to be biodegradable
(Bastioli, 2005). There are several studies on biodegradability
of PVOH in composting (Fishman et al., 2006) and aqueous
media (Larking et al., 1999). Normally PVOH material de-
grades faster in the composting environment than in the water
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environment. The rate and extent of PVOH biodegradation can
be increased by Pycnoporus cinnabarinus, followed by preoxi-
dation of PVOH with Fenton’s reagent. Celanese Chemicals,
one of the PVOH manufacturers, confirmed PVOH biodegrad-
ability, and the specific PVOH biodegradation information can
be found at its corporate website (http://www.celanese.com).
The date to access the information was December 10, 2010.
To improve the melt processing issues of PVOH, we found
that inorganic fillers such as calcium carbonate and talc,
respectively, were able to resolve the pronounced adhesion
and fogging of volatile plasticizer during the melt extrusion of
PVOH to form dispersible resin pellets and conduct film cast-
For personal use only.
ing. In practice, sodium aluminosilicate is also used as filler,
together with crosslinking agents such as maleic acid and glu-
taraldehyde to produce PVOH membrane (Singha, et al.,
2009). Filled PVOH is also less expensive and a cost reduction
depends on the amount of the filler integrated. On the other
hand, film mechanical properties decrease as filler increased.
Therefore, a good balance is desirable in order to tailor the
need of film physical properties and film cost. This paper ad-
dresses the compositions, processing conditions, and properties
of the PVOH films from these studies. The final selection has
been made according to several comparisons of CaCO3 and
talc filled water-soluble films for additional processing and
commercial scale-up operations.
2 Experimental
2.1 Materials
Celvol 523S was PVOH purchased from Celanese Chemicals
(Dallas, TX). The degree of hydrolysis for Celvol 523S is
88 %. The number and weight averaged molecular weights are
61,900 and 148,300 g/mol, respectively. The polydisperity in-
dex is 2.4. The melting point is 180 * 230 8C. Glycerin was
used as a plasticizer and purchased from Cognis Corporation
(Cincinnati, OH). Two filler materials were used: 1) Omyacarb
2sst grade of CaCO3 was purchased from Omya, Inc. (Proctor,
VT). It has a 2.0 lm median particle size and is well coated
with a stearic acid treatment, and 2) talc was purchased from
Barretts Minerals (Bethlehem, PA). It is known as
H2Mg3(SiO3)4, which corresponds to 4.8 % H2O; 31.7 %
MgO, and 63.5 % SiO2.
232
2.2 Equipment
ZSK-30 Twin Screw Extruder (Werner and Pfleiderer Cor-
poration, Ramsey, NJ) is a co-rotating, twin screw extruder.
The extruder diameter was 30 mm with a screw length of
1 328 mm. A 3-hole die was used to form strands for pelletiz-
ing. The pellets produced from ZSK-30 were then made into
blown films using HAAKE Rheomex 252 Single Screw Ex-
truder with a die attachment.
Göttfert Rheograph 2003 capillary rheometer (Rock Hill,
SC) was used for melt rheology of the filled PVOH pellets.
MTS Sintech 1/D Tensile Tester is an apparatus from which
film mechanical tensile data was obtained together with the
TestWorks 4 program.
A \slosh box" is a standard device made at Kimberly-Clark
to test film, fiber, and tissue water disintegration (Wang and
Funk, 2009; Shi and Wang, 2009; and Dyer et al., 2010). It
has a physical dimension of a 120 cm · 46 cm · 30 cm
plastic box on a hinged platform. The one end of the platform
is attached to the reciprocating cam. The typical amplitude is
 5 cm (10 cm range), with sloshing occurring at
0.5 * 1.5 sloshes per second. The preferred action is
0.9 * 1.3 sloshes per second. The time is recorded and re-
ported when film is dissolved in water.
2.3 Plasticizing
PVOH was supplied as granules. The first step in the melt pro-
cessing was to convert it into pellets using glycerin as a plasti-
cizer. The operational setup temperatures on ZSK-30 from
zones 1 to 7 were from 100, 160, 185, 190, 180, 170, and
165 8C, respectively. The screw speed was set to 190 min – 1,
with a melting temperature range of 155 to 165 8C and a pres-
sure range of 1,378 to 3,447 KN/m2 observed during the extru-
sion process. The torque was approximately 40 %. The higher
the percent of glycerin used, the lower the torque became. Gly-
cerin was pumped at 10, 15, and 20 %. It was found that glycer-
in at 20 % was the best to pelletizing PVOH for water-soluble
film applications, which was a level of plasticizer used in all
experiments. A three-hole die was used throughout the com-
pounding process. The resin strands produced by the ZSK-30
were cooled on a cooling belt by a series of fans. Once the resin
had cooled, it was pelletized and stored in plastic bags.
2.4 Compounding
A similar process as PVOH plasticizing was done during
PVOH compounding. The PVOH component was run through
a feeder manufactured by K-Tron (Pitman, NJ) and the filler
(2sst CaCO3) or talc was fed into the extruder via a side-feeder.
The feed rate of the side-feeder was adjusted to change the
amount of filler present in the final blend.
The temperature profile was similar to those used in PVOH
plasticizing operations shown above. The screw speed for
ZSK-30 was set to 140 min – 1. The melting temperature ranged
from 170 to 190 8C, the pressure ranged from 1,654 to
1,861 kN/m2. The torque for the converting screw fluctuated
around 30 to 40 %.
Intern. Polymer Processing XXVII (2012) 2
 B. Shi et al.: Improving the Processability of Water-soluble Films

2.5 Melt Viscosity 2.9 Film Water Solubility Test

Plasticized PVOH pellets with and without inorganic fillers
were tested to attain material melt viscosity using a Göttfert
Rheograph 2003 capillary rheometer (Rock Hill, SC). The
PVOH resin was added into the capillary rheomter when it
was heated to 190 8C. A program was used to control the rate
of the piston that pushes the PVOH material through a die and
the melt viscosity was recorded.
2.6 Blown Film
Blown films were made using the HAAKE Rheomex 252 Sin-
gle Screw Extruder fitted an annular film die to form a film
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The rate of film disintegration in tap water was tested using a
\slosh box" (Wang and Funk, 2009). During a test, the slosh
box rocks up and down with the water inside, \sloshing" back
and forth. This action produces a wave front and intermittent
motion on a sample susceptible to dispersing in water. To
quantify a measurement of sample film disintegration in water,
without image analysis, simply timing is sufficient (Shi and
Wang, 2009; Dyer et al., 2010). Three liters of tap water at am-
bient room temperature (21 8C) were added into the slosh box
and resulted in *14 cm water depth in the box. A frequency
of sloshing was 1.3 sloshes per second during the testing. Each
film sample with its thickness at 30 micrometer was cut into
2.5 cm (W) · 7.5 cm (L) size. Three pieces were dropped into
the slosh box. The time to disintegrate the sample under the de-

bubble which was cooled and collected. The temperature pro-

file from zones 1 to 5 was 180, 185, 190, 188, and 185 8C, re-
spectively. The screw speed was set to 45 min – 1. The pressure
ranged from 4,137 to 6,894 kN/m2 and the torque was approxi-
mately 1 200 N m. These values were altered slightly for each
blend. The melting temperature was around 197 8C. All films
were conditioned in a temperature and humidity controlled
room, where the temperature and humidity were fixed at
22.8 8C and 50 % RH, respectively. Samples were placed in
closed plastic bags during conditioning for a day prior to be
tested.
For personal use only.
fined conditions was recorded twice for each sample. The aver-
age of the time to the sample disintegration is then reported.
3 Results and Discussion
3.1 Melt Rheology
Fig. 1 shows the data for plasticized PVOH-Celvol 523S/gly-
cerin (80/20), which is abbreviated as P-Celvol 523S, CaCO3
filled PVOH-P-Celvol 523S+10 % 2sst CaCO3 (Celvol 523S/
glycerin (80/20)+10 % 2sst CaCO3), and talc filled PVOH-P-

Celvol 523S+10 % talc (Celvol 523S/glycerin (80/20)+10 %

2.7 Scanning Electron Microscopy
talc), respectively. The results obtained at 190 8C confirm that
all three samples exhibited shear thinning behavior, which is
The filled PVOH film samples with 10 % CaCO3 and talc, re-
commonly observed for thermoplastic materials. The melt
spectively, were selected for a scanning electron microscopy
viscosity is the highest for talc filled PVOH, followed by the
(SEM) study. The photograph was obtained by a plasma etch-
unfilled PVOH. The CaCO3 filled PVOH has the lowest
ing/optical method using the standard secondary electron im-
viscosity. It is believed that the differences in the melt rheology
aging mode achieved by a positive-biased detector (e. g. an
between calcium carbonate filled PVOH and talc filled PVOH
Everhart-Thornley detector). The samples were immersed in
are at least partially due to the particle size difference between
ethanol, frozen by immersion in liquid nitrogen, and impact-
particle sizes of the fillers, the calcium carbonate had a smaller
sectioned with a single edge razor blade while in the liquid ni-
average particle diameter of 2.0 lm, while talc has average
trogen and placed on a metal surface to reach room temperature
particle diameter of 2.5 lm. It is understandable that material
for a direct examination.

2.8 Tensile Property Test

All tensile properties were tested on the MTS Sintech 1/D Ten-
sile testing apparatus. Samples were prepared for testing by
taking a portion of the film, and cutting five dog-bone shaped
samples in each direction (MD and CD). The test length of
each dog-bone was 18 mm, the width in the center was 3 mm,
and the thickness varied around 25 lm. Each dog-bone was
tested separately. During the test, samples were stretched at a
crosshead speed of 127 mm/min until breakage occurred. The
computer program TestWorks 4 collected data points during
the testing and generated a stress (MPa) versus strain (%) curve
from which a variety of properties were determined: modulus,
peak stress, elongation, and toughness.
All data represented the mean of five independent experi-
ments. Error bars shown in figures are standard deviations cal-
culated using a method outlined by Young (1996). Fig. 1. Melt viscosity of filled and unfilled PVOH

Intern. Polymer Processing XXVII (2012) 2 233

 B. Shi et al.: Improving the Processability of Water-soluble Films
processing would be challenged for the talc filled PVOH be-
cause of the high melt viscosity value.
The melting and glass transition temperatures for the filled
PVOH blends are about 180 and 29 8C, respectively. These
values are affected by amount of the plasticizer in the blends,
with little effect due to the presence of different types of filler.
3.2 Resolving PVOH Film Adhesion Issue
By extruding PVOH blends containing from 5 to 10 % CaCO3
or talc, it was observed that the adhesion of the neat plasticized
PVOH film to process equipment surface was eliminated. One
of the reasons for adhesion elimination is due to the presence of
CaCO3 or talc filler on the surface of the films, resulting in re-
duced adhesion of the microscopically uneven surface.
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3.3 Filled PVOH Modulus
Talc and calcium carbonate fillers were incorporated, respec-
tively, into the PVOH in order to reduce the cost and adhesion
of the PVOH material. The amount of talc and calcium carbo-
nate incorporated was fixed at 5, 10, and 15 % of the water-so-
luble films. All charts for y-axis and x-axis were plotted on
the same scale for easy comparisons.
The blown films created from P-Celvol 523S with either talc
or CaCO3 filler were soft and pliable, but not sticky during or
after film processing. Fig. 2 shows the machine-direction
For personal use only.
(MD) (left) and cross-direction (CD) (right) moduli of three
different P-Celvol 523S blends with different percentages of
talc or calcium carbonate filler. One standard deviation based
on five (5) dog-bone sample data was plotted and shown in
the chart as well.
A significant increase in the MD film modulus was observed
at 15 % talc (p << 0.05). It is more than doubled in comparison
A) B)
A) B)
234
to the PVOH film containing 10 % talc and more than tripled in
comparison to the PVOH film containing 5 % talc, while the in-
crease in CD film modulus is also doubled. The PVOH film
modulus is fairly stable when CaCO3 was used and the results
are shown in Fig. 2. A higher film modulus generally indicates
a rigidity of the water-soluble films. The CD film modulus is
fairly stable, showing there is no difference in talc and CaCO3.
At 15 % talc, the deviation of the MD film modulus is the
greatest, which is more pronounced in comparison to the same
level (15 %) of 2sst CaCO3 as filler. The reason for this obser-
vation is due to a particle size difference in mineral fillers. Talc
used for this study has an average particle size of 2.5 lm
whereas 2sst CaCO3 has an average particle size of 2.0 lm.
Another factor to account for the deviation is that 2sst CaCO3
is coated by an anionic dispersant at low levels so that PVOH
and 2sst CaCO3 is intermixed better than when talc was used,
which is uncoated. In addition, it can be seen in Fig. 2 that the
CD film modulus deviated not as dramatic as in MD, which in-
dicated the directionally-induced effects for film modulus en-
hancement.
3.4 Filled PVOH Peak Stress
Fig. 3 indicates the peak stresses of these films. The film peak
stress is not affected dramatically by a change in amount of in-
organic filler. In general, the PVOH is stronger when CaCO3
was present. In comparison, talc filled PVOH films have
slightly lower film peak stress than those films filled by
CaCO3, regardless of whether it is the film MD or CD mechan-
ical properties. The maximum film peak stress was achieved at
10 % filler except for the film with 5 % CaCO3 as filler in the
film cross direction. The filled MD film peak stress is at 80
and 61 MPa for 5 % of CaCO3 and talc, respectively. At 15 %
CaCO3, the filled CD film peak stress decreases about 12 % as
the filler is increased from 5 to 15 %. Similarly, talc filled CD
Fig. 2. Film modulus comparisons of P-Cel-
vol 523S filled with talc (A) or 2sst CaCO3
(B), respectively
Fig. 3. Film peak stress comparison of P-Cel-
vol 523S filled with talc (A) or 2sst CaCO3 (B),
respectively
Intern. Polymer Processing XXVII (2012) 2
 B. Shi et al.: Improving the Processability of Water-soluble Films
film stress reduced about 14 %. Wang and Qi (2010) found the
maximum peak stress occurred at 5 % CaCO3 filler and film
mechanical property decreases as filler increased. In this study,
the maximum MD peak stress is at 10 % filler level. The reason
is likely due to different grades of CaCO3 filler materials.
Normally the desirable film peak stress requirement for
flushable products (an example of flushable product is the wet
wipe when it is after the use, it can be disposed into a toilet
and flushed) ranges from 20 to 50 MPa. For all water soluble
films based on filled thermoplastic polyvinyl alcohol, their
peak stresses meet the application requirements irrespective to
types of the filler. Therefore, the film peak stress information
may not be critical in a final selection of the filler for additional
scale-up work.
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3.5 Filled PVOH Elongation
Fig. 4 represents the film elongation-at-break. At 15 % CaCO3
filler, the film MD elongation started to decrease as expected.
Overall, these films possess ductility rather than brittleness re-
gardless of a variation of amount calcium carbonate from 5 to
15 %.
Clearly the film elongation is decreased as the amount of
talc is increased in the PVOH films. However, film CD elonga-
tion was relatively stable within the range of talc addition, i. e.,
from 5 to 15 %. This is due to the fact that film machine direc-
tion is stretched more than film cross direction during the
For personal use only.
blown film making process. The reduced stretching in the CD
masked the weakness even though the talc is increased from 5
to 15 %. A comparison of the film CD elongation to those of
CaCO3 filled PVOH films, the CD elongations in Fig. 4 are
similar at 5 and 15 %, but not at 10 % CaCO3 filler level. How-
A) B)
Fig. 5. A Cross-sectional view of the PVOH film (MD) with 10 % 2sst
CaCO3 filler
Intern. Polymer Processing XXVII (2012) 2
ever, film MD elongation when talc was present is inferior to
those of CaCO3 filled PVOH films. At 15 % talc, the film MD
elongation reduced 52 % from the talc at 5 % level, and it is
only 15 % reduction for the CaCO3 filled PVOH films in
machine direction. Therefore, the CaCO3 is the preferred inor-
ganic filler on a basis of elongation comparison of the filled
PVOH films.
This investigation to resolve PVOH adhesion issue revealed
that P-Celvol 523S possessed the required tensile strength and
film elongation for product applications. The film had the ten-
dency to curl up on itself when it was cut. This made the test-
ing a daunting task. This curling behavior may be due to the
film's low modulus (softness), which could be resolved if a
combination of plasticizers were used. In addition to the ease
of processing, preference is given to CaCO3 because the filled
PVOH film mechanical properties are not significantly af-
fected by changes in amount of filler presented in the PVOH
blends.
3.6 Film Structure
The film cross-sectional views were based on the film machine
direction and shown whereas the SEM view on the film cross
direction was similar and not shown for a sake of brevity. The
results are shown in Fig. 5 for the PVOH film filled with 10 %
CaCO3 as filler, which approximated spheres. Fig. 6 for the
PVOH film filled with 10 % talc as filler, showing a layered
collection of plates. The presence of fillers and some filler ag-
gregates visible in the films led to tortuous pathway for water
to penetrate to the interior of the film and thus delay the water
solubility in comparison to the neat PVOH films that are dis-
solved instantly upon contact with water.
Fig. 4. Film elongation comparison of P-Cel-
vol 523S filled with talc (A) or 2sst CaCO3
(B), respectively
Fig. 6. A Cross-sectional view of the PVOH film (MD) with 10 % talc
filler
235
 B. Shi et al.: Improving the Processability of Water-soluble Films
3.7 Filled PVOH Water Solubility
All three films disintegrated in the slosh box within 7 to
10 minutes of contact with water. The pure PVOH film dis-
persed immediately upon a contact with water. The delayed
water solubility may actually be beneficial for certain packa-
ging applications such as packaging bags for pesticide, herbi-
cide, fertilizers during shipping and storage.
4 Conclusions
Water soluble films based on polyvinyl alcohol were econom-
ically produced through an extrusion technology. The PVOH
material adhesion issue has been resolved by addition of the in-
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organic filler such as calcium carbonate or talc. The trade off by
addition of the filler results in high melt viscosity for talc filled
PVOH and lower melt viscosity for calcium carbonate filled
PVOH, which needs to be adjusted during film processing.
The PVOH film cost can be reduced by incorporation of in-
organic filler while the film adhesion to processing equipment
is eliminated. These water-soluble films are potential candi-
dates for water-dispersible film applications such as packaging
of toxic pesticide, etc.
According to film aging studies conducted by Meisel and
Wang (2007), glycerin is the preferred choice because plastici-
zer migration is not observed. The recommended amount of fil-
ler to add into Celvol 523S material is about 10 % CaCO3,
For personal use only.
which provides a good balance among film processability, cost
and mechanical properties.
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DOI 10.3139/217.2517
Intern. Polymer Processing
XXVII (2012) 2; page 231 – 236
ª Carl Hanser Verlag GmbH & Co. KG
ISSN 0930-777X
You will find the article and additional material by enter-
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Intern. Polymer Processing XXVII (2012) 2