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Journal of Polymers and the Environment, Vol. 14, No.

1, January 2006 ( 2006)


DOI: 10.1007/s10924-005-8709-8

Mechanical Properties with the Functional Group of Additives


for Starch/PVA Blend Film
Yeon-Hum Yun,1 Young-Ho Na,2 and Soon-Do Yoon2,3

This paper deals with the mechanical properties and degree of swelling (DS) of starch/PVA
blend lm with the functional groups i.e., hydroxyl and carboxyl group, of additives. Starch/
PVA blend lms were prepared by using the mixing process. Glycerol (GL) with 3 hydroxyl
group, sorbitol (SO) with 6 hydroxyl group, succinic acid (SA) with 2 carboxyl group, malic
acid (MA) with 1 hydroxyl and 2 carboxyl group, tartaric acid (TA) with 2 hydroxyl and 2
carboxyl group and citric acid (CA) with 1 hydroxyl and 3 carboxyl group were used as
additives. The results of measured tensile strength (TS) and elongation (%E) veried that both
hydroxyl and carboxyl group as a functional groups increased the exibility and strength of
the lm. Values of DS for GL-added and SA-added lms were low. However, DS values of the
lms added MA, TA or CA with both hydroxyl and carboxyl group were comparatively high.
When the lm was dried at low temperature, the properties of the lms were evidently improved. The reason is probably because the hydrogen bonding was activated at low
temperature.
KEY WORDS: Starch/PVA blend lm; functional group; additives; mechanical properties; degree of
swelling.

to fossil resources and global environment is


thorough recycling wasted polymeric materials. The
recycling of wasted plastics is limited, whether
materials recycling or chemical recycling consumes
a considerable amount of thermal energy, and plastics cannot be recycled forever, that is, wasted plastics are eventually destined to be burnt or buried in
landlls [1, 2].
Biodegradable plastics which can be easily
degraded in a natural environment are gaining public interest [3, 4]. They are designed to be easily
destroyed and to nally disappear in a natural environment such as landll sites.
Starch is a high molecular-weight polymer of
anhydroglucose units linked by alpha-D glycoside
bonds. The two major polymers in starch are amylose and amylopectin. Amylose is a linear molecule
with an extended helical twist. Amylopektin is a

INTRODUCTION
Nowadays, about 150 million tons of plastics
are produced annually all over the world, and the
production and consumption continue to increase.
Most of these plastics are crude oil based, and an
increase in their production results in an increase of
oil use and causes serious environmental pollution,
due to wasted and undegraded polymers. One of
the strategies to solve the difcult questions related
1

Department of Mineral & Energy Resources Engineering,


Chonnam National University, 300 Yongbong-dong, Buk-gu,
Kwangju 500-757, South Korea.
Department of Applied Chemical Engineering, Chonnam
National University, 300 Yongbong-dong, Buk-gu, Kwangju
500-757, South Korea.
To whom all correspondence should be addressed. E-mail:
yunsd03@empal.com

71
1566-2543/06/0100-00071/0  2006 Springer Science+Business Media, Inc.

72

Yun, Na, and Yoon


fruits and plants. However, its richest source is
apples, which is why it is sometimes referred to
as apple acid. It is blended with multiple food
acids, sugars, high intensity sweeteners, avors,
and seasonings to create unique tastes in foods,
beverages, and confections. TA with 2 hydroxyl
and 2 carboxyl group is the strongest and most
important acid present in grapes and also in
wines. Its concentration (usually 25 g/l) is decisive in the definition of the acidity of wines, thus
affecting its characteristics such as odor, color
and flavor. CA with 1 hydroxyl and 3 carboxyl
group appears in a natural way in foods like citrus fruits and pineapples where it is the main organic acid. CA is utilized as multi-functional food
additive in the processes of producing different
foods because it presents antibacterial and acidulant effect, reinforces the antioxidant action of
other substances, and improves the flavors of juices, soft drinks and syrups. Starch/PVA blend
film was prepared by the mixing process.
The mechanical properties (TS and %E) and
degree of swelling (DS) were measured for synthesized starch/PVA blend lms using GL, SO, SA,
MA, TA and CA as additives.

branched molecule. Amylose is generally smaller


molecules with molecular weight of 11.5 million.
Amylopektin are by comparison large with a molecular weight of 50500 million [5].
The research showed that after starch was lled
in or blended with synthesized polymer, the synthetic fraction from the oil source has not better
susceptibility to biodegradation [68]. So the most
recent research has focused on pure starch-based
materials and starch/degradable polymer blend
materials such as starch/cellulose, starch/polyvinyl
alcohol (PVA) [912].
The inuence of starch sources, starch components, starch molecular mass and plasticizer, such as
water and polyols, has been studied to improve the
mechanical properties of starch plastics. However,
poor mechanical properties constituted one of the
major unresolved problems. Although their tensile
strength (TS) may be rather high (3060 MPa),
these materials are fragile with low elongation at
break and poor water resistance. After absorbing
water, they were very weak and could not be used
[1318].
In this study, The properties of lms with the
functional group of additives were compared.
Glycerol (GL), sorbitol (SO), succinic acid (SA),
malic acid (MA), tartaric acid (TA) and citric
acid (CA) were used for additives. The structure
of each additives is represented in Fig. 1. SO with
6 hydroxyl group is an alcohol sugar widely used
in the food industry, not only as a sweetener but
also as a humectant, texturizer, and softener. SA
with 2 carboxyl group is a dicarboxylic acid, and
has received a great deal of attention as a green
feed stock for the manufacture of synthetic resins,
biodegradable polymers, and chemical intermediates [19]. MA with 1 hydroxyl and 2 carboxyl
group is a naturally occurring substance in many

EXPERIMENTAL
Materials
Starch (cornstarch) was obtained from Doosan
Corn Products Korea, Inc. (Korea). PVA, reagent
grade GL, SO, SA, MA, TA and CA were purchased from Aldrich chemical company Inc.(Milwaukee, USA). PVA was 99% hydrolyzed with a
molecular weight average of 89,00098,000. The
water used to prepare starch/PVA blend films was
redistilled after deionization.

OH
HO

OH

OH

HO
OH

OH

HO

OH

OH
(b)

OH

HO

OH
OH
(d)

(a)

OH

(c)

HO

OH
O

OH
(e)

OH

HO
O
HO

OH
O

(f)

Fig. 1. Chemical structures of the additives used in this work. (a) GL; (b) SO; (c) SA; (d) MA; (e) TA; (f) CA.

Mechanical Properties with the Functional Group

73
pre-warmed (75C) teon mould (200 200
2 mm). Water was evaporated from the moulds in a
ventilated oven at 50C for 12 hour and in a cold
lab. chamber at 5C for 72 hour. Dried lms were
put in open polyethylene bags and stored at 20C
and at RH 53% for 1 week before the measurements were made performed.

Preparation of Starch/PVA Blend Film


Films were obtained by the casting method. At
rst, PVA solution was prepared by dissolving PVA
in hot water (95C). Starch and additives (GL, SO,
SA, MA, TA and CA) were mixed together with
water using a Kitchenaid mixer for 10 minute. Formulations contained 10, 20, 30, 40 and 50% GL,
SO, SA, MA, TA and CA (weight basis). PVA
solution and mixed starch/additives were kept at
95C for 5 minute. Then, the mixture was blended
to form homogeneously gel-like solution with a
mechanical stirrer (1200 rpm) at room temperature
for 50 minute. The total polymer amount was
100 g. Starch and PVA had the same mass ratio,
and the content of additives was expressed as mass
percent ratio of additives to total starch and PVA
weight, respectively. Bubbles, the by-product of
preparation, were removed by using an aspirator.
The mixing composition is shown in Table I. The
gel-like solution thus prepared was poured on a

Mechanical Properties of Starch/PVA Blend Film


TS and elongation (%E) were evaluated for
each lm using an Instron 6012 testing machine.
Four dumbbell shaped specimens (ASTM D-421)
were cut from each lm. Specimens had a width of
16 mm. Each piece was measured for thickness in
three places along the test length using a Mitutoyo
(Japan). The specimens average thickness was
about 0.2 mm. Both gauge length and grip distance
were 50.0 mm. Crosshead speed was 20 mm/minute
and load cell was 25 kgf. The tests were carried out

Table I. Composition of Starch/PVA Blend Films


Sample name
SP
SPGL10
SPGL20
SPGL30
SPGL40
SPGL50
SPSO10
SPSO20
SPSO30
SPSO40
SPSO50
SPSA10
SPSA20
SPSA30
SPSA40
SPSA50
SPMA10
SPMA20
SPMA30
SPMA40
SPMA50
SPTA10
SPTA20
SPTA30
SPTA40
SPTA50
SPCA10
SPCA20
SPCA30
SPCA40
SPCA50

Starch

PVA

5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%

5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%
5%

GL

10
20
30
40
50

wt.%
wt.%
wt.%
wt.%
wt.%

SO

10
20
30
40
50

wt.%
wt.%
wt.%
wt.%
wt.%

SA

10
20
30
40
50

wt.%
wt.%
wt.%
wt.%
wt.%

MA

10
20
30
40
50

wt.%
wt.%
wt.%
wt.%
wt.%

TA

10
20
30
40
50

CA

wt.%
wt.%
wt.%
wt.%
wt.%

10
20
30
40
50

wt.%
wt.%
wt.%
wt.%
wt.%

74

Yun, Na, and Yoon

at 20C and 53% RH in a constant temperature and


humidity room.
DS of Starch/PVA Blend Film
Dried starch/PVA blend lms were immersed in
distilled water at room temperature (25C). After
the equilibrium is attained after about 24 hour,
moisture on the surface of the lm was removed,
and the weight of the lm was measured. The DS in
starch/PVA blend lm was calculated from the
equation:
DS We  W0 =W0
where, We is the weight of starch/PVA blend lm at
the adsorbing equilibrium, and W0 is the weight of
dry starch/PVA blend lm before absorbing water.

Fig. 3. TS of starch/PVA blend lms adding GL, SO, SA, MA,


TA and CA as additives.

RESULTS AND DISCUSSION


Mechanical Properties of Starch/PVA Blend Film
Figure 2 shows the variations of TS and elongation (%E) of the lm using starch and PVA without additives. Starch and PVA contents are 5% of
total weight of polymer, respectively. TS and %E
were equilibrated over 40 minute, and their values
after equilibrium were 55.58 MPa and 20.27%. By
considering this result, starch/PVA blend lms with
additives (GL, SO, SA, MA, TA and CA) were
prepared by the mixing process.
Figures 3 and 4 show, respectively, the results
of TS and %E of lms to which 10, 20, 30, 40 and
50 wt.% GL, SO SA, MA, TA and CA are added.

20
70
15
60
10

Elongation(%)

Tensile strength(MPa)

Fig. 4. Elongation (%E) of starch/PVA blend lms adding GL,


SO, SA, MA, TA and CA as additives.

25

80

50
5

40
0

20

40

60

80

100

0
120

Mixing time(min)
Fig. 2. TS and elongation (%E) of starch/PVA blend lm versus
mixing time.

As the contents of GL, SO, MA, TA and CA increased from 10 to 50 wt.%, TS decreased while %E
increased. However, in the SA-added lm TS increased while %E decreased, as the content of SA
increased.
The comparison of results between the GL
(with 2 hydroxyl group)-added and SA (with 2 carboxyl group)-added starch/PVA blend lms showed
that TS of GL-added lm was lower than SA-added
lm when the same contents were added. However,
%E of GL-added lm was higher than that of SAadded lm. SA-added lms were too brittle to apply.
Also, the results of comparison between the
GL and SO (with 6 hydroxyl group)-added lms

Mechanical Properties with the Functional Group


showed that TS and %E of SO-added lm were
higher than GL-added lm.
For the lm containing MA with 1 hydroxyl
and 2 carboxyl group, TS and %E were higher than
GL-added and SO-added lms. Films containing
TA with 2 hydroxyl and 2 carboxyl groups have
higher TS and %E than GL-added, SO-added and
MA-added lms. We also observed that the starch/
PVA blend lm added CA composed of 1 hydroxyl
group and 3 carboxyl groups showed the best performance in TS and %E.
When the additive with both hydroxyl and carboxyl groups were simultaneously added, it was observed that TS and %E were better than GL-added
and SO-added lm with hydroxyl group only.
These lms are synthesized by hydrogen bonding between starch, PVA and additives. We found
that MA, TA and CA with hydroxyl group and
carboxyl group are stronger than GL or SO with
only hydroxyl group in hydrogen bonding between
starch PVA and additional materials molecules.
In other to conrm the relation on the functional groups i.e, hydroxyl and carboxyl group, the
additives were mixed and added to starch/PVA
blend lm. Table II shows composition of starch/
PVA blend lm adding the mixed additives.
Figures 5 and 6 show the results of TS and %E for
starch/PVA lm containing both the mixed additives GL-SA and SO-SA in the same contents. %E
of the GL-SA-added and SO-SA lms increased
while that of SA-added lm decreased as the content of additive increased. On the other hand, TS of
GL-SA-added and SO-SA-added lms decreased
while that of SA-added lm decreased as the content of additive increased. The results of TS and
%E of GL-SA-added and SO-SA-added lms
revealed that the addition of the additives with

Table II. Composition of Starch/PVA Blend Films Adding


Mixed Additives
Sample name
SPGLSA10
SPGLSA20
SPGLSA30
SPGLSA40
SPGLSA50
SPSOSA10
SPSOSA20
SPSOSA30
SPSOSA40
SPSOSA50

Starch

PVA

GL

SO

SA

5%
5%
5%
5%
5%
5%
5%
5%
5%
5%

5%
5%
5%
5%
5%
5%
5%
5%
5%
5%

5 wt.%
10 wt.%
15 wt.%
20 wt.%
25 wt.%

5 wt.%
10 wt.%
15 wt.%
20 wt.%
25 wt.%

5 wt.%
10 wt.%
15 wt.%
20 wt.%
25 wt.%
5 wt.%
10 wt.%
15 wt.%
20 wt.%
25 wt.%

75

Fig. 5. TS of starch/PVA blend lms adding GL, SO, SA, GLSA and SO-SA as additives. where, SPGL is lm added GL,
SPSO is lm added SO, SPSA is lm added SA, SPGLSA is lm
added GL-SA as the mixed additives, SPSOSA is lm SO-SA as
the mixed additives.

Fig. 6. Elongation (%E) of starch/PVA blend lms adding GL,


SO, SA, GL-SA and SO-SA as additives. where, SPGL is lm
added GL, SPSO is lm added SO, SPSA is lm added SA,
SPGLSA is lm added GL-SA as the mixed additives, SPSOSA
is lm SO-SA as the mixed additives.

hydroxyl and carboxyl group as a functional group


increased the exibility and strength of lms.
Table III shows the results of TS and %E of
starch/PVA blend lm after drying at 50 and 5C.
Compared to the starch/PVA blend lm to which
additives of the same contents were added, TS and
%E of the lm dried at 5C were higher than those
of the lm dried at 50C. It is considered that the

76

Yun, Na, and Yoon

Table III. TS and Elongation (%E) of Drying Starch/PVA Blend


Films at 50 and 5C
Sample name

TS (MPa)

Elongation (%)

SP
SP
SPGL30
SPGL30
SPSO30
SPSO30
SPSA30
SPSA30
SPMA30
SPMA30
SPTA30
SPTA30
SPCA30
SPCA30
SPGLSA30
SPGLSA30
SPSOSA30
SPSOSA30

55.58
60.97
7.3
8.5
9.3
10.42
68.7
70
13.1
15.79
17.4
19.19
32.39
35.3
24.6
26.9
35
37.88

20.27
40.74
87.7
93.6
97.2
100.7
5.12
6.39
108.1
120.6
126
140.2
141.9
162.9
48.31
53.39
58.7
62.18

Fig. 8. DS of starch/PVA blend lms adding GL, SO, SA, MA,


TA and CA as additives.

Where, SP, SPGL30, SPSO30, SPSA30, SPMA30, SPTA30,


SPCA30, SPGLSA30 and SPSOSA30 are lms dried at 5C.

reason is because hydrogen bonding was activated


at the lower temperature.
DS of Starch/PVA Blend Film
DS of the starch/PVA blend lm without
additive are shown in Fig. 7. As the mixing time
increased, DS was decreased rapidly and
equilibrated after 40 minute. This phenomenon occurred because free volume decreased due to the
formation of hydrogen bonding between starch
and PVA.

Fig. 9. DS of starch/PVA blend lms adding GL, SO, SA, GLSA and SO-SA as additives. where, SPGL is lm added GL,
SPSO is lm added SO, SPSA is lm added SA, SPGLSA is lm
added GL-SA as the mixed additives, SPSOSA is lm SO-SA as
the mixed additives.

Fig. 7. DS of starch/PVA blend lm versus mixing time.

Also, the mean lm was not formed until the


mixing time of 2040 minute passed. When the film
is was mixed over 40 minute, equilibrium DS value
was 2.8, respectively.
In Fig. 8, with the increase in the content of
GL, SO, SA, MA, TA and CA as additives, DS of
starch/PVA blend lms decreased slightly. Starch/
PVA blend lms containing both GL with hydroxyl
group and SA with carboxyl group added showed
lower DS values.

Mechanical Properties with the Functional Group

77

Fig. 10. DS of drying starch/PVA blend lms at 50 and 5C. Where, SP, SPGL30, SPSO30, SPSA30, SPMA30, SPTA30 and
SPCA30 are lms dried at 5C.

DS values of the lms to which MA with 2 carboxyl and 1 hydroxyl group, TA with 2 carboxyl
and 2 hydroxyl group and CA with 3 carboxyl and
1 hydroxyl group as the functional group had a
comparatively high value. As the number of the
carboxyl and hydroxyl group of additive increased,
DS values increased. DS value increases because
MA, TA and CA are easily soluble and combine
with H2O molecule and attributed to the hydrophilism of PVA, MA, TA and CA.
Figure 9 represents the DS values of lms prepared by adding the same content GL-SA and
SO-SA in starch/PVA blend lms. DS values of
GL-SA-added and SO-SA-added lm were lower
than those of GL-added, SO-added and SA-added
lms. These results showed the same characteristics
as those of the MA-added TA-added and CA-added
lms.
DS values of the starch/PVA blend lms
dried at 50 and 5C are shown in Fig. 10. When
the same contents of GL, SO, SA, MA and TA
was added to additive, the lms dried at 5C
showed low DS value. As discussed earlier, DS
values are low because hydrogen bonding is activated at low temperature.

CONCLUSIONS
Starch/PVA blend lms were prepared successfully by using starch, PVA, GL, SO, SA, MA, TA
and CA for the mixing process. Materials with hydroxyl and carboxyl group as functional group
cross-linked between starch and PVA were used to
as additive for starch/PVA blend lms. Values of
TS and %E were investigated. The results veried
that hydroxyl and carboxyl group as a functional
group increased the exibility and strength of the
lms. DS values of the MA-added or TA-added
lms were higher than GL-added, SO-added and
SA-added lms. The reason is because materials
having both hydroxyl and carboxyl group, i.e., MA,
TA or CA are the highly hydrophilic.
TS, %E and DS values were superior when the
lm was dried at 5C than at 50C. This is considered to result from the occurrence of hydrogen
bonding at the lower temperature.
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