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Arturo J. Mendoza
School of Engineering & Materials Science, Queen Mary University of London, London E1 4NS, United Kingdom

Modification of starch by cross-linking is used in many fields, as the process improves many of the properties of
starch, yet most cross-linking agents in common use tend to be toxic, expensive, or both. Polycarboxylic acids
could function as nontoxic alternatives to these – some, such as tartaric acid (TA), are also less expensive. This
study presents a method to cross-link thermoplastic starch films with TA, as well as the effect of this modification
on the tensile strength of the material when films are prepared using different reaction conditions. An increase
in strength was observed, which is believed to occur due to an increase in the London dispersion forces acting
within the cross-linked starch (CLS). The greatest observed increase in the maximum tensile strength of the
plastic was 6%. Monosodium tartrate was used as a catalyst for the cross-linking reaction. The maximum tensile
strengths of the plastics produced were determined by using adapted binder clips, a hook (total mass 10g) and
hanging masses to subject films of the plastics to progressively greater tension. Incremental weights of 10g were
used, with recorded tensions at fracture of 1.2~8.9 N.
La modification d’amidon à l’aide de réticulation est utilisée dans de nombreux domaines puisque ce processus
améliore un grand nombre des propriétés de l’amidon, cependant un grand nombre des agents de réticulation
d’usage courant ont tendance à être toxiques, couteux, ou les deux. Les acides polycarboxyliques pourraient être
utilisé en tant qu’alternatifs non toxiques pour ceux-ci – certains, tel l’acide tartrique (TA) sont disponible à faible
coût. L’étude présente un procédé afin de réticuler des pellicules thermoplastiques d’amidon avec la TA, ainsi
que l’effet de cette modification sur la résistance à la traction du matériel lorsque les pellicules sont préparées à
l’aide de différentes conditions réactionnelles. Une augmentation de la force fut remarquée, et on estime que ceci
se produire en raison d’une augmentation des forces de dispersion de LONDON agissant dans l’amidon réticulé.
L’augmentation la plus proéminente de la résistance à la traction maximale de la matière plastique observée
fut de 6%. Le tartrate monosodique fut comme catalyseur pour la réaction de réticulation. Les résistances à la
traction maximale des matières plastiques produits furent déterminées par l’utilisation d’attaches adaptées, un
crochet (masse total de 10g) et des masses suspendus afin de soumettre des pellicules de matières plastiques
à une tension progressivement plus grande. Des poids incrémentaux de 10g furent utilisés, avec des tensions
enregistrées à la rupture de 1,2 ~ 8,9 N.
Starch is a polysaccharide found in the amyloplasts of to acidic conditions, heat, shear, and an increase in
most green plants[1]. It is composed of amylose (linear) the gelatinization temperature of starch[2-5]. These
and amylopectin (branched) molecules, the proportions phenomena have been related to a reduction in the
of which vary depending on the source. Cross-linking number of hydroxyl functional groups in the material
starch is the process of forming intermolecular and the reduced mobility of amylose and amylopectin
bridges between the D-glucose units in amylose and within the amorphous phases of starch granules due
amylopectin. This modification of starch is used for to the presence of intermolecular bridges[2, 6-8].
a range of food and non-food related applications. However, the applications of cross-linked starch (CLS)
Effects appealing to the food industry include a are not limited to the food industry. Improvements
reduction in the rate of retrogradation and resulting in the resistance to dissolution in water and acidic
synereses of starch, and an increased resistance media could allow CLS plastics to be biodegradable

alternatives to many of the oil-based plastics MATERIALS AND METHODS
commonly used in packaging[9-11]. Moreover, most Reagent-grade sodium carbonate, L(+) tartaric
CLS plastics are edible, making edible packaging acid, and glycerol were purchased from Merck SA,
another possible application[2]. Caracas, Venezuela. Distilled water was purchased
Most cross-linking agents currently used in the from Himelab Distribuidora CA, Caracas, Venezuela.
modification of starch are toxic. Nontoxic alternatives Corn starch was purchased from Citadino CA,
include polycarboxylic acids. These can be used to Caracas, Venezuela.
produce a safer product for use in food applications [2, 6, 12]. Film Preparation
Polycarboxylic acids cross-link through esterification
reactions between hydroxyl functional groups in the A solution of 0.75 mol/L TA and 0.09 mol/L MT was
D-glucose units of starch and the carboxylic acid prepared by adding sodium carbonate to aqueous TA.
terminal of the acids[6]. This solution was used to prepare 300 mL solutions
with the required concentrations of TA for the different
Some of these acids are of low cost, which could cross-linking reactions. Starch was dispersed in these
make them attractive in commercial environments solutions as a 3% weight fraction. These dispersions
when compared with commonly used cross-linkers were heated to and maintained at 90oC for 20 minutes
such as epichlorohydrin[12, 13-16]. on a hotplate. Afterwards, they were cooled to 60oC
Tartaric acid (TA) is a viable cross-linking agent and the required amount of 4.89 mol/L glycerol
for usage in the modification of starch, exhibiting solution was added to them. The mixtures were then
similar effects on modified starch hydrogels as other stirred and poured onto polished polystyrene plates.
cross-linking agents[17]. The main positive attribute The mixtures air-dried at 22 ± 3 oC for 72 hours. The
of TA is that it can be recovered from winemaking resulting cast films were then peeled off from the
wastewater through relatively cheap processes[18-28]. substrates before being cured in a non-fan-assisted
Approximately 8 × 106 m3 of wine wastewater is oven at 165 oC on borosilicate trays for the required
produced each year in Spain - 6 times more than amounts of time. The films were then conditioned for
the wine wastewater produced in France or Italy; this 48 hours at 22 ± 3 oC and 70 ± 10% relative humidity.
represents an enormous potential supply of TA[23].
Tensile Testing
This study investigates the effect the cross-linking
conditions of starch on the maximum tensile strength Two 10 cm by 1 cm strips were cut from each film
(MTS) of cast CLS plastic films obtained using TA as a in different directions. The MTS of each strip was
cross-linking agent. Moreover, an optimal combination determined as follows: its ends were clamped by a
of these conditions is herein investigated such that binder clip modified with electrical tape for improved
the MTS of produced films is maximized while TA is grip. One of these clips was nailed to a shelf. A metal
used as the cross-linking agent. The fundamental hook was slid through the other. Weights were loaded
hypothesis of this investigation is that varying these on this hook in 10 g increments. The load each film was
parameters will affect the MTS of solution-cast CLS subjected to at failure was used in calculating its MTS.
plastic films. For this calculation, the thickness of each film was
Aqueous solutions of corn starch, glycerol TA and measured thus: a square section of film was folded
catalyst were used for casting. The catalyst chosen five times. The edges of this folded structure were cut
for usage was monosodium tartrate (MT), which off and its height was measured using a ruler precise
was prepared in situ[29]. The parameters considered to 0.25 mm. This height was divided by 32 to obtain
were the weight fractions of glycerol and TA in the the average thickness of the film. This value was
solution prior to casting, and the time for which the used to calculate the MTS of the film. The range of
films were cured at 165oC after casting in order for the measured heights was 2.75 ± 0.75 mm.
esterification reactions to take place.

Effect of Glycerol
Glycerol is well known as a plasticizer. The glycerol
percentage of a cast plastic film (with respect to
the mass of starch used) has an effect on its MTS
(Figure 1). Both control and cross-linked films without
glycerol were too brittle to be tested. An increase in
the glycerol content from 5% to 10% results in an
increase of the MTS of tested films. Further increases
in glycerol content cause films to exhibit progressively
lower MTS values. This trend continues up to the
greatest trialled content: 30%.
Qualitative observations suggest the elongation at
break shown by a cross-linked starch plastic varies
positively with the weight fraction of glycerol present
in the same. Figure 1: The optimal weight fraction of glycerol is 10%. Maximum tensile strength tests
Figure 1:
were carried out on samples synthesized with 5% tartaric acid weight fractions that were
Effect of Tartaric Acid Theforoptimal
cured weightdifferent
5 minutes, containing fraction of weight
glycerol glycerol is Two
fractions. 10%. Maximum
strips were cut from
Films cross-linked with different TA weight fractions each film and tested in random directions and their average maximum tensile strength was
tensile strength tests were carried out on samples synthesized
calculated. Error bars are shown. The relationship between the average maximum tensile
(with respect to the mass of starch used) exhibited with 5% tartaric acid weight fractions that were cured for
strength of these films and their glycerol weight fraction is depicted.
different MTS (Figure 2). An initial increase in TA 5 minutes, containing different glycerol weight fractions.
content from 0% to 1% causes a decrease in the MTS Two strips were cut from each film and tested in random
of cast films. Further increases in TA content up to directions and their average maximum tensile strength was
calculated. Error bars are shown. The relationship between
5% bring about an increase in the films’ MTS, which
the average maximum tensile strength of these films and
reach a maximum at 12.2 ± 0.6 MPa. This represents
their glycerol weight fraction is depicted.
a gain of 19.6 ± 6% in the MTS of the plastic as
compared to the value measured for the film without
TA. Increasing the TA weight fraction beyond 5% the progressive loading phase of the tensile test they
decreases the MTS of cast films. This trend continues were subject to. The deformation behaviour exhibited
through to the highest tested TA weight fraction: 15%. by a sample containing 10% glycerol and 7% TA
Effect of Curing Times which was not cured was remarkable in that it was
very similar to that of the films containing 25% and
The relationship between the time for which a film is 30% glycerol and 5% TA weight fractions, but which
cured at 165oC and its MTS was studied (Figure 3). It had been cured for 5 minutes.
can be seen that there exists a range of curing times
(3 to 5 minutes) where the variation in MTS is small. Samples that were cured for 8 and 10 minutes
This is also the region where the maximum MTS was developed a yellow colour and a smell similar to that
observed: for the samples that underwent 5 minutes of of burnt sugar. This change in colour and smell was
curing. A second set of trials was carried out for films greater in samples that were cured for 10 minutes.
containing 10% glycerol and 7% TA weight fractions. Cross-Linking Effectiveness
For these, the optimal curing time was found to be the Evidence is herein presented that suggests cross-
same, with the maximum exhibited MTS being 9 MPa. linking takes place at a significant rate with the
Unreacted TA that remains in the films after the curing methodology used in this study (Figure 4). It shows
process may function as a plasticizer. Samples cured the MTS of a control film made of non-cured
for shorter periods exhibited more elongation at thermoplastic starch (TPS) with 10% glycerol and
break, and greater elastic deformation throughout no TA. Figure 4 also shows the effect that curing an

Figure 2: The optimal weight fraction of tartaric acid is 5%. Maximum tensile strength tests Figure 3: The optimal curing time is 5 minutes. Maximum tensile strength tests were
Figure 2:out on samples synthesized with 10% glycerol weight fractions, which were
were carried Figure
carried out3:
on samples synthesized with a 10% glycerol weight fraction and a 5% tartaric
cured for 5 minutes, containing different tartaric acid fractions. Two strips were cut from acid weight fraction that were cured for different periods of time. Two strips were cut from
The optimal
each film weight
tested in random fraction
directions of tartaric
and their average acidstrength
maximum tensile is 5%.
was The optimal
each film and testedcuring time is
in random directions and5their
minutes. Maximum
average maximum tensile
tensile strength was
calculated. Errortensile
bars are strength tests were
shown. The relationship betweencarried outmaximum
the average on samples
tensile strength tests
calculated. Error were
bars are shown.carried out between
The relationship on samples
the average synthesized
maximum tensile
strength of these films and their tartaric acid fraction is depicted. strength of these films and the time for which they were cured is depicted.
synthesized with 10% glycerol weight fractions, which with a 10% glycerol weight fraction and a 5% tartaric acid
were cured for 5 minutes, containing different tartaric acid weight fraction that were cured for different periods of time.
fractions. Two strips were cut from each film tested in random Two strips were cut from each film and tested in random
directions and their average maximum tensile strength was directions and their average maximum tensile strength was
calculated. Error bars are shown. The relationship between calculated. Error bars are shown. The relationship between
the average maximum tensile strength of these films and the average maximum tensile strength of these films and the
their tartaric acid fraction is depicted. time for which they were cured is depicted.


identical TPS sample for 5 minutes has on its MTS.

Likewise, it depicts the effect that the presence of a
5% weight fraction of TA has on the MTS of another 10

identical sample that was not cured. Both of these are


substantial reductions in the plastic’s MTS: 11.5% ±
7% and 37% ± 4% due to curing and the presence of 6

TA respectively. However, when a TPS sample with

a 5% weight fraction of TA is cured for 5 minutes, an
increase of 6% ± 5% from the control film’s baseline 2

MTS is observed.

Effectiveness of the Catalyst Used A: 0% TA, 0 Minutes

B: 0% TA, 5 Minutes
C: 5% TA, 0 Minutes
D: 5% TA, 5 Minutes
Sample Code & Reaction Conditions
Significant variation of MTS with curing time was
observed for samples containing TA. This suggests Figure 4:
the rate of the esterification reaction during curing A comparison of maximum tensile strengths suggests
was significant. Hence, a mass of monosodium cross-Linking took place under the used conditions.
tartrate equal to 13.8% of the used TA mass would be Maximum tensile strength tests were carried out on four
effective as a catalyst for the cross-linking of starch samples (A, B, C, D) all of which had 10% glycerol weight
when TA is used as a cross-linking agent. fractions. Neither sample A nor B had tartaric acid weight
fractions. Sample B was cured for 5 minutes while sample
A wasn not cured. Samples C and D both had 5% tartaric
acid weight fractions, but sample D was cured for 5 minutes
while sample C wasn’t cured

Optimal Synthesis Parameters: The Presence of Cross-Links
The optimal conditions used during cross-linking to Figures 2 and 3 suggest that increases in the number
obtain films with the largest MTS were found to be: of cross-links in CLS initially increase its MTS. This
Weight fractions of 10% and 5% of glycerol and TA could be due to an increase in the London dispersion
respectively, and a curing time of 5 minutes. This forces (LDFs) in the material: if amylose and
combination yielded a CLS plastic film of a MTS of amylopectin molecules became cross-linked, their
12.2 ± 0.6 MPa. resulting molecular weight would be larger. Hence,
DISCUSSION the LDFs experienced by CLS molecules should
be greater than those experienced by amylose and
The way the reaction conditions affect the MTS amylopectin in native starch. This could increase the
of cast films can be explained through theories MTS of the macroscopic material.
proposed in existing research. In these, the mobility
and molecular weight of the constituent molecules of Figure 3 also suggests that excessive cross-links
CLS is given importance. have a negative effect on the MTS of CLS. This could
be attributed to cross-linked molecules having less
Glycerol and TA as Plasticisers mobility than unmodified amylose and amylopectin.
The results show that adding glycerol to CLS initially Curing Weakens Films
increases its MTS, but further additions result in a
drop in MTS. This could be explained by a progressive This study corroborates that curing will degrade TPS,
increase in the mobility of the CLS molecules – where weakening films and producing changes in colour[6]. Also,
films were conditioned for 48 hours after being cured as
this is caused by an increased distance between these,
otherwise; they were too brittle to be tested. This could
resulting from having the plasticizers embed between
be attributed to evaporation of water in the films during
CLS molecules and forming hydrogen bonds with their
curing since water also has a plasticizer effect. If so,
hydroxyl terminals. It must be noted that not all hydroxyl
after the water present in a film has evaporated during
functional groups in amylose and amylopectin act as
curing, its amylose, amylopectin and CLS molecules
sites of esterification during the curing process, and
would be heated at a greater rate and hence degrade
hence remain hydroxyls in CLS [17].
more quickly. This might explain the very low MTS of
It is possible that a small number of plasticizer films that were cured for 8 and 10 minutes.
molecules provide CLS molecules with enough
mobility to rearrange when subject to stress. The CONCLUSION
macroscopic effect of this would be the exhibition This analysis proposes that a critical degree of mobility
of elastic and plastic deformation[30, 31]. However, an must be reached in CLS for its MTS to be maximized.
excess of plasticizers could separate CLS molecules The optimal set of reaction conditions balances the
to a point where the intermolecular forces they converse effects of cross-links and plasticizers on
experience are significantly reduced. This could the mobility of CLS molecules while keeping their
cause a reduction in the MTS of the material[6, 32, 33]. LDFs as large as possible. At the same time, these
The elongations at break of the tested films were conditions must minimize the thermal degradation to
qualitatively recorded as comparative observations the material during curing.
while the MTS tests were carried out. However, FUTURE DIRECTIONS
existing research shows that glycerol content While the present study explores the ways the MTS of
increases the elongation at break of CLS films using CLS made with TA is affected by the reaction conditions
a similar polycarboxylic acid as the cross-linking used, there remains a range of this material’s properties
agent[6]. The usage of glycerol and polycarboxylic that have not been studied herein.
acids as plasticisers in other bioplastic systems is
well documented[30-34]. It would be of interest to investigate the reduced
solubility of TA-CLS in acidic conditions, since this is

typically one of the improvements of cross-linking on 5. Kaur, M; Oberoi, D. P. S; Sogi, D. S; Gill, B.
thermoplastic starch[6]. Likewise, the thermal properties, S. Physico-Chemical, Morphological and Pasting
Young’s modulus, yield behaviour, permeability and Properties of Acid Treated Starches from different
morphology of these films could be investigated. Botanical Sources. J. Food Sci. Technol. [Online]
The effectiveness of catalysts other than monosodium 2011, 48, 460–465.
tartrate when TA is used could be further investigated. 6. Wang, Y. J; Wang, L. Physicochemical Properties
Many are expected to be effective[29, 35, 36]. of Common and Waxy Corn Starches Oxidized
The processability of CLS plastics (TA-based or by different levels of Sodium Hypochlorite.
otherwise) has not been investigated in detail. Carbohydr. Polym. [Online] 2003, 52, 207–217.
However, it would be of interest to determine the 7. Narendra, R; Yiqi, Y. Citric acid cross-linking of
effects of cross-links in this regard, since this is a very starch films. Food Chem. [Online] 2009, 118, 702-
important material characteristic in industry. 711. doi:10.1016/j.foodchem.2009.05.050
ABBREVIATIONS 8. Raina, C. S; Singh, S; Bawa, A. S; Saxena, D.
TA Tartaric Acid C. Some characteristics of acetylated, cross-linked
and dual modified Indian rice starches. Eur. Food
CLS Cross-Linked Starch Res. Technol. 2006, 223, 561–570.
MTS Maximum Tensile Strength 9. Sobolewska-ZielińskaJ.,FortunaT.Retrogradation
MT Monosodium Tartrate of starches and maltodextrins of origin various.
Acta Sci. Pol., Technol. Aliment. 2010, 9, 71-81.
10. Ayoub A. S; Rizvi. S. S. H. An Overview on
The author would like to thank Mr Gordon Watson- the Technology of Cross-Linking of Starch
Broughton, Dr Lorenzo Botto, Dr Helena Azevedo, for Nonfood Applications. Journal of Plastic
Dr Emiliano Bilotti and Dr Remzi Becer for their Film and Sheeting 2009 [Online] 00, 1-22
guidance in the writing of this paper. doi:10.1177/8756087909336493
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