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IC-CMTP6 IOP Publishing
Journal of Physics: Conference Series 2315 (2022) 012036 doi:10.1088/1742-6596/2315/1/012036

Crosslinking of Starch Using Citric Acid

A G Gerezgiher1, T Szabó1
1
Department of Materials Sciences and Engineering, University of Miskolc, Hungary.

E-mail: [email protected] and [email protected]

Abstract. With a purpose of improving mainly the water resistivity and related physical and
mechanical property of starch biopolymer, citric acid was used to modify the chemical structure
of starch by crosslinking the polymer chains. Corn starch films were produced first dispersing
4% (w/w) starch in water, adding glycerol (36% of the weight of starch) and citric acid (20% of
the weight starch) successively allowing them to react at different pH. Water absorption, FTIR,
DMA, DSC and SEM tests were done to characterize the thin film samples. Results showed that
availability of glycerol is a critical factor for the crosslinking and plasticity property of the film.
Samples prepared with citric acid crosslinked starch without the inclusion of glycerol were brittle
and has easily disintegrated in water as crystals. The crosslinking reaction done under acidic
condition was found more effective than the other reactions. Generally, citric acid has effectively
crosslinked corn starch polymer molecules reducing the amount of hydroxyl group in their
structure. As a result improvement in the water resistant is observed.
Keywords: Citric acid, Crosslinking, Starch, biopolymers

1. Introduction
Materials are being continuously and exponentially modified and improved in all fields of use, such as
polymers [1–6], ceramics [7–10] and so on. Crosslinking is one of the most popular methodes to alter
the behavior of biodegradable starch polymers [11, 12]. Crosslinking or cross-ligation is interconnection
of linear or branched chains in a polymer. Ether or ester bonds are formed when the reagents react with
the hydroxyl groups in starch molecules crosslinking process [13]. This modification increases the
polymer’s rigidity by forming a three-dimensional network. Crosslinking in starch increases the degree
of polymerization and molecular mass; starch molecules lose water solubility and become soluble in
organic solvents. Several agents are used to crosslink native starch: sodium trimetaphosphate (STMP),
sodium tripolyphosphate (STPP), epichlorohydrin (ECH) and phosphoryl chloride (POCl 3), among
others [14–17]. Polysaccharides containing hydroxyl groups have the possibility to be crosslinked by
poly-functional carboxylic acids. Examples of poly-carboxylic acids that have been used to cross-link
polysaccharide materials are 1, 2, 3, 4-butanetetracarboxylic acid [18, 19], poly (maleic acid) [19] and
citric acid [18]. Some examples of polysaccharide materials which have been crosslinked with poly-
carboxylic acids are starch granules [20], starch nanoparticles [21], starch films [22], starch gels [23].
In all these studies, the reaction temperature is high, well above 100 °C and long reaction times (minutes)
are used. This is because of the slow reaction kinetics of esterification of poly-carboxylic acids with
hydroxyl groups on polymers due to the low amount of poly-carboxylic acid used.
Citric acid has the possibility to react with two or more of the hydroxyl groups present in the starch.
One good reason for using citric acid as a cross-linker is due to the fact that the unreacted citric acid
(CA) is considered nutritionally harmless and may also act as a plasticizer for starch [24–26].

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Journal of Physics: Conference Series 2315 (2022) 012036 doi:10.1088/1742-6596/2315/1/012036

The esterification cross-linking reaction between citric acid and starch can be performed at both acidic
and basic conditions. For acidic conditions, known as Fischer esterification, the esterification reaction
is an equilibrium-controlled reaction between a carboxylic acid group and a hydroxyl group. The
reaction starts with protonation of the carboxylic acid group, which in turn can be attacked by the alcohol
group forming an ester. In this reaction, water is produced as a by-product that limits the equilibrium
unless it is evaporated [27]. The reaction can be performed both with and without additional catalysts.
Often the catalyst is a strong inorganic acid. The acid used as the catalyst needs to be stronger than the
poly-carboxylic acid to be esterified otherwise excessive neutralization of the catalyst will retard the
crosslinking reaction. The catalyst should be able to neutralize the carboxylic acid group, but not vice
versa [18, 28]. It has been indicated that it is not the addition of catalysts as such, but rather that the pH
was the important factor for the esterification reaction to take place [29].
Citric acid has been used for the increment of hydrophobicity of starch by crosslinking it under dry
reaction. The citric acid crosslinked starch was found to have greater affinity for low Polar solvents like
dichloromethane It was found that the crosslinked starch nanocrystals displayed a higher affinity for low
polar solvents such as dichloromethane [30].
Adding citric acid to biodegradable starch has improved the thermal stability, water resistant and
fluidity due to the strong hydrogen bond created between starch and citric acid. Citric acid has negatively
influenced the tensile stress and has also prevented starch from recrystallization and widens the
processing temperature of starch [31]. Citric acid is also reported to increase the plasticity of starch by
first depolymerizing the starch granules when added with water and glycerol [32]. Hydrolysis of starch
solution in the presence of citric acid is highly influenced by citric acid concentration, reaction
temperature and pH during crosslinking [33]. This experimental work is designed to cross link citric
acid with different processing approaches and inputs so as to maily improve its water resistivity.

2. Experimental [3]
2.1 Materials
Corn starch was obtained from HAAS Naturals with 100% corn starch having moisture content of 11.4%
and ash content 0.14%. Citric acid (food grade) was obtained from Herman Ker Bt. Hungary. Plant
Glycerin with pharmaceutical quality was obtained from Flora Vita, Kévés Béla Kft (PhEur.9.0, USP
Pharmacy quality. Natural vegetable, 99.5% pure, Glycerin E422). HCL and NaOH chemicals were also
prepared for adjusting the pH of the solution during mixing and improve the reactivity.

2.2 Fabrication of Cross-linked Starch Samples

Corn starch films were produced by first dispersing 4% (w/w) starch in water. The starch dispersion was
heated in a heater at 90 °C and was kept at this temperature for 20 minutes while stirring rigorously
using the magnetic stirrer. Then, glycerol 36% by weight of the starch was added and heated at the same
temperature for 10 minutes until a transparent and viscous slurry is formed. NaOH was added to increase
the pH from 6.5 to 11. Litmus paper was used to check and determine the pH of the dispersion. Then
after, citric acid 20% by weight of the starch was added to the dispersion and heating was continued for
another 20 minutes and finally HCL acid 0.1 mol was used to neutralize the solution.
The solution was poured into Teflon coated tray and kept in a furnace at 65 °C for 48 hours. Plasticized
and cross-linked starch film with 0.5mm thick was peeled from the tray and prepared for
experimentation.

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Journal of Physics: Conference Series 2315 (2022) 012036 doi:10.1088/1742-6596/2315/1/012036

Figure 1. Pictorial representation of starch film production process

Table 1. Starch film samples prepared

S.No. Designation of Description
Samples
produced
1 CS Starch cross linked with citric acid, no glycerin added.
2 TPS Thermoplastic starch, without citric acid
3 HTPS Cross linked thermoplastic starch with citric acid as a cross linker; and
NaOH and HCL acid as pH adjustment. Cross linking was done at a pH
of 12 and then neutralized to 7 pH.
4 CCTPS CTPS prepared by adding starch, water, glycerol, NaOH and citric acid.
Reaction was done at a pH of 6 and cured under a furnace at 165 °C for
10 minutes (cured CTPS)
5 NCTPS CTPS without curing (non-cured CTPS)
6 3CTPS Cross linked TPS with citric acid. Reactions held at a pH of 3. Without
adding NaOH and HCL, no pH adjustment
7 ATPS TPS film was prepared. The film was put in a tray having a solution of
3:7 citric acid to alcohol ratio. The film in the solution was put in furnace
for 48 hours at 75 °C.
8 WS Water and Starch Solution

3. Characterization and Testing Methodology

3.1 Water Absorption

The water absorption capacity of starch composites crosslinked with various concentrations of citric
acid was measured according to ASTM Test Method D570: Standard Test Method for Water Absorption
of Plastics at room temperature. The samples were cut into small pieces (30*20*0.5 mm), put into oven,
and dried at 110 °C for 24 h. Then, they were taken out and weighted. The dried samples were immersed
in distilled water and their final weight measured. The water content (K) was calculated from the
following equation:
𝑤2−𝑤1
𝐾 = 𝑤1 (1)
Where w1= the initial weight of the sample,
w2= is the final weight of the sample after it is immersed to the distilled water.

3.2 Fourier Transformed Infrared Test (FTIR)

The FTIR spectrum of the samples were tested using Bruker FTIR instrument (BRUKER, Germany)
using diamond disk technique at the faculty of materials science and engineering, institute of ceramic
and polymer engineering, university of Miskolc. A resolution of 4 cm-1 with a spectral range of 4000-
400 cm-1was used. 64 scans were done to collect each spectrum.

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IC-CMTP6 IOP Publishing
Journal of Physics: Conference Series 2315 (2022) 012036 doi:10.1088/1742-6596/2315/1/012036

3.3 Dynamic Mechanical Analysis (DMA) Test

Samples (45×5×0.5mm) were cut from the prepared starch films. DMA measurements were performed
using a PerkinElmer DMA 8000. Measurements were per-formed under flowing air at frequency of
1 Hz, with a maximum dynamic force of 2 N, amplitudes up to 16mm.The temperature is hold for
1.0 minute at -100.00 °C and Heated from -100 °C to 60 °C with a heating rate of 2 °C/min.

3.4 Differential Scanning Calorimetry (DSC) Test

The heat flow measurement was made using Perkin Elmer DSC131 Evo. The thermoplastic starch
composite specimens of nearly 10 mg mass were heated from 20 to 200 °C at a rate of 10 °C min-1 and
then cooled at the same rate to 20 °C, waited at 20 °C for 5 minutes, finally reheated to 200 °C.

3.5 Scanning Electron Microscope (SEM) Test

To study the phase morphology, an EVO MA 10 scanning electron microscope (Carl Zeiss, Germany)
was used. The equipment was operated at an acceleration voltage of 20 kV. To prevent electrical charge
during observation, a thin layer of gold was coated to the samples. Images were taken of the fractured
surface at the magnification of 1,000X.

4. Result and Interpretation

4.1 Water Absorption

Native starch is hydrophilic and crosslinking of the starch chains after plasticization by citric acid is
expected to reduce the water absorption rate. Fig.2 shows that all the samples have high absorption rate
in the first 20 minutes of wetting time. It is also evident in fig. 2.2 that the non-plasticized (WS) has the
highest water absorption rate in the first 20 minutes and has started dissolving at about 20 minutes. This
indicates that plasticization of starch with glycerin has a positive effect on reducing the hydrophilicity
of non-modified starch. 3CTPS (citric acid, starch film sample produced at a lower pH 3), NCTPS (non-
cured; citric acid, starch film sample produced at about 6 pH) has got lower water absorption rate when
compared with the CCTPS (CTPS cured at 165 °C for 10 minutes.). This shows that curing of the
samples has negatively affected the water absorption property of the starch film. Curing might have
created cracks or pores on the sample. The three samples prepared adding citric acid as a cross-linker;
CCTPS, NCTS and 3CTPS has lower water absorption rate and have started dissolving latter than TPS,
WS, HCTPS and ACTPS. This is an evidence that esterification reaction has occurred, and this reaction
has reduced free hydroxyl groups which in turn reduced the hydrophilicity. The results have confirmed
what was reported by Heebthong et.al, Jutarat et.al, Olsson et.al [34-36]. The technique of crosslinking
the surface of the starch film which was used to produce sample ACTPS don’t alter the hydrophilicity
of the starch.

140
120 HCTPS
Water Absorption %

100 TPS
80 CCTPS
60 NCTPS
40 3CTPS
20 ACTPS
0 WS
0 0,3 1,2 2,2 18 24 60 72
Wetting Time (hr)

Figure 2. Water Absorption Test Result

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Journal of Physics: Conference Series 2315 (2022) 012036 doi:10.1088/1742-6596/2315/1/012036

4.2. Fourier Transform Infrared Spectroscopy (FTIR) Result

Fig. 3, shows the FTIR spectra of the samples (non-cross linked/cross linked starch samples) with citric
acid under different techniques. The FTIR spectrum of all the samples shows characteristic IR bands of
starch at 572, 830, 994, 1076, 1149, 1336, 1411, 1643, 2925 and broad band at 3278 cm-1. Two of the
characteristic bands mentioned 994 and 1076 cm-1 could be due to the C-O bond stretching band [37].
And 1149 cm-1 can be attributed due to the asymmetric vibration of C-O-C bonds, which shows the
formation of ether bonds that decreases the hydrophilicity of starch. The band 2925 cm-1 is due to the
symmetric and asymmetric vibration of C-H bond. The broad band 3278 cm-1 is assigned to the hydroxyl
groups of starch. Among the seven samples tested FTIR spectra of 1723 cm -1 has appeared on CS,
CCTPS, NCTPS, and 3CTPS samples, while the same spectra is not seen on the samples TPS, ACTPS
and HCTPS samples. The availability/appearance of 1723 cm-1 on CS, CCTPS, NCTPS, and 3CTPS
samples shows the formation of ester groups as a result of cross linking [38, 39]. The result of the FTIR
test generally shows that TPS which is free of citric acid, ACTS (sample prepared by immersing TPS
into a solution of citric acid and alcohol) and HCTPS (sample prepared at pH 12) are not cross linked,
which means the techniques followed don’t favor crosslinking to happen. Samples CS (a sample
prepared without glycerin as a plasticizer); and samples CCTPS, NCTPS, and 3CTPS prepared at a pH
below 6 are cross linked.

Figure 3. Fourier Transform Infrared Spectroscopy (FTIR) Spectrum of samples

4.3 Dynamic Mechanical Analyzer (DMA) Result

Fig. 4, below shows the dynamic mechanical analysis result of the prepared samples. The curves mainly
represent the modulus (loss modulus and storage modulus) and Tan δ (the ratio between the storage
modulus and loss modulus). This test is mainly used in this research to determine the stiffness and
viscoelastic property of the samples. Tan δ curves shows the internal friction of mechanical damping in
the system. An increase in the value of Tan δ value shows that the material is viscous, and a value low
shows that the material is elastic. Tan δ curve of the samples TPS and ACTPS has sharp picks each at -
50.47 oC and (-64.56 °C and 7.22 °C) respectively. The Tan δ curve of the samples 3CTPS, NCTPS,
HCTPS and CCTPS shows single sharp picks at 12.72 °C, 12.84 °C, 11.42 °C, and 3.27 °C respectively.
The sharp peak on the Tan δ curve normally shows the glass transition temperature (Tg) of the materials.
The glass transition temperature of the cross linked samples is shifted to a higher temperature due to the
effect of cross linking by citric acid than the non-cross linked TPS and ACTPS which prepared in a
different technique.

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Journal of Physics: Conference Series 2315 (2022) 012036 doi:10.1088/1742-6596/2315/1/012036

The Tan δ curve shown in the fig.4, generally is higher for 3CTPS, NCTPS, HCTPS and CCTPS and
lower for TPS and ACTPS. This also could be due to the cross linking of the samples by citric acid,
which in turn has increased the viscosity of the materia [40].
Fig.4 also shows the comparison of the of the storage modulus curves for all samples tested. The
storage modulus of the samples TPS and ACTPS is less than the storage modulus of NCTPS, CCTPS
and HCTPS. This shows that the crosslinked samples are stiffer than the noncrosslinked samples. This
result is consistent with the finding of Simões, Bruno Matheus et.al. [40].

Figure 4. Dynamic mechanical analyzer (DMA) thermogram of samples

4.4 Morphology
The morphology of the starch film samples prepared under different conditions and variable agents is
studied by Scanning electron microscope (SEM) magnified 1000X and the results are presented in Fig.5.
Samples TPS and CCTPS shows similarity in their surface morphology that looks like an entangled
polymer chain. This result indicates that the addition of glycerin to the samples has helped in
plasticization and as a consequence long chains are formed. This also indicates that curing of starch
films at 165 °C during preparation has a negative effect on crosslinking. The morphology of HCTPS
shows agglomerations of NaCl gained from the reactions when NaOH and HCL are added to increase
and decrease the pH of the system respectively. This has negatively affected the crosslinking
performance and related properties. The morphology of ACTPS is also like TPS, but the solution of
citric acid and alcohol which the sample was immersed in do not allow a clear image of the surface of
the starch film. The morphology of the starch film samples CS, 3CTPS, NCTPS show a homogenies
and similar picture, showing the uniform dispersion and crosslinking of the starch granules.
Crosslinking has modified the size and aggregation of the starch granules.

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IC-CMTP6 IOP Publishing
Journal of Physics: Conference Series 2315 (2022) 012036 doi:10.1088/1742-6596/2315/1/012036

A) 3CTPS B) ACTPS

C) CCTPS D) CS

E) HCTPS F) NCTPS

G) TPS H) WS
Figure 5. SEM scans of samples

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Journal of Physics: Conference Series 2315 (2022) 012036 doi:10.1088/1742-6596/2315/1/012036

4.5. Thermal Analysis Using Differential Scanning Calorimetry (DSC)

Fig. 6, shows the DSC thermogram of the films (samples) prepared by mixing citric acid as a
crosslinking agent and the free films without citric acid. The DSC thermogram collected at the first
heating cycle is the curve indicated below and the DSC thermogram collected at the second heating
cycle is situated above the first heating cycle curve for all the samples tested. All the sample films have
an endothermic peak at about 120 °C both on the first and second heating cycles which is against the
finding by Reddy et. al. [22] which states a shift of the endothermic peaks of the cross-linked films to a
higher temperature when compared with non-cross-linked films in the DSC thermogram. The
appearance of the endothermic peaks both in the first and second heating cycles on all the samples
indicates that there is a reversible temperature sensitive structural change which is not affected by
availability of the cross-linking agent. On the same DSC thermogram, TPS has showed a second
endothermic peak (Tm) at about 170 °C, this could be due to plasticization of the starch by glycerin
which changed the semi crystal structure of starch in to more amorphous structures with lesser melting
point. Except TPS, all the other starch film doesn’t show a second endothermic peak (Tm) at the
specified range, the shifting of the second endothermic peak (Tm) to higher level on the starch film
samples indicates that the inclusion of citric acid as a cross-linking and/or as impurity has affected to
the increase in the melting point of starch films.

A) NCTPS B) WS C) CTPS

D) ACTPS E) 3CTPS F) CS

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Journal of Physics: Conference Series 2315 (2022) 012036 doi:10.1088/1742-6596/2315/1/012036

G) TPS H) HCTPS
Figure 6. DSC thermograms of samples

5. Conclusion
Starch film samples prepared using different techniques and reagents were characterized for their water
absorption, surface morphology, thermal and mechanical property, and structural change. Samples
3CTPS, NCTPS and HCTPS are prepared at 3, 6, and 12 pH respectively, to assess the effect of pH on
crosslinking potential. Crosslinking was found better on NCTPS and 3CTPS, but lower on HCTPS. This
shows that crosslinking/esterification reaction of among citric acid, glycerin and starch is better achieved
at lower pH and much better when done at about 6 pH. Samples NCTPS and CCTPS were prepared to
evaluate the effect of curing on crosslinking potential. CCTPS is sample NCTPS cured at 165 °C for 10
minutes. Result has indicated that NCTPS is better crosslinked than CCTPS; which is against most of
the reports done on this area, even if some reports have also supported this finding. ACTPS was prepared
in a new and innovative method to crosslink the surface of the TPS film immersing it in to a solution of
citric acid and alcohol at about 70 °C, but currently results are showing no significant change in property
compared to the controlled TPS sample. CTPS, and CS are prepared to assess the effect of glycerin on
the degree of crosslinking. Results showed that availability of glycerin is a critical factor for the
crosslinking and plasticity property of the film. CS samples were brittle and has easily disintegrated in
water as crystals. Generally, citric acid has increased the water resistance of starch crosslinking the
chains of starch molecules and reducing the amount of hydroxyl group.

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