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SEAWEED A SUSTAINABLE SOURCE FOR BIOPLASTIC: A REVIEW

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SEAWEED A SUSTAINABLE SOURCE FOR BIOPLASTIC: A REVIEW


Shravya S C*1, Vybhava Lakshmi N*2, Pooja P*3, Kishore Kumar C M*4,
Sadashiva Murthy B M*5
*1,2,3,44th Year Students, Department Of Environmental Engineering, JSS Science And Technology
University, Mysuru. India.
*5Professor, Department Of Environmental Engineering, JSS Science And Technology
University, Mysuru. India.
ABSTRACT
Nowadays Petroleum-based plastics have become a part of living and we can find plastics everywhere on earth
from oceans to human placenta. Hence it is necessary to find an alternative degradable plastic from renewable
sources. In this paper, we have reviewed the biodegradable seaweed-based bioplastic with different
seaweed/starch/cellulose proportions along with the plasticizers and its impact on the physical properties and
characteristics of the biofilm. The method involved in biofilm synthesis is also studied. Replacement of single
use plastic in food packing and also other applications are discussed. Seaweed based bioplastic is eco friendly in
nature as it is completely degradable in soil. Besides the great mechanical properties and shorter shelf life,
seaweed based bioplastic would be a better chance to overcome the plastic pollution.
Keywords: Seaweed; Biofilm; Biodegradability; Polysaccharide; Starch; Cellulose.
I. INTRODUCTION
Petroleum based plastics are increasing day by day because of human demand and because of its versatility,
these non biodegradable plastics travel from land, river and ocean [48]. These plastics take several thousand
years to degrade, these plastics break down into nano particles and also enter the guts of fishes and birds and
human placenta [9] . The cause for increase in the plastic pollution is due to improper waste management and
awareness among the people. Hence renewable sources like plants(corn, starch, rice, sweet potato, sugarcane),
bacteria(Bacillus megaterium, Klebsiella aerogenes, Pseudomonas aeroginosa), algal(microalgae like Spirulina
dregs, macroalgae like Seaweeds) and seaweeds(Chlorophyta,Pheophyta, Rhodophyta) can be used as an
alternative source for plastic, because of its biodegradability, eco-friendly and edibility [22][38]. Preferably
bioplastic can be synthesised from seaweed because they are rich in polysaccharides and which are widely used
in the field of food technology, microbiology, biotechnology and even in medicine but not widely used in the
plastic industry [51]. Since seaweed is a renewable Biomass resource and are polymers made from sugars
which contain carbon they could be used to create biodegradable high quality bioplastic, it aims to make a good
environmentally friendly, inexpensive and toxic free bioplast [31][49]. Fig.1. Indicates the Global Plastic
production in 2019 was 368 million metric tons. In 2020 The plastic production decreased around 0.3% due to
Covid 19 impact on the industry[6][47]. The main objective of the paper is to compare the properties of the
biofilm synthesised with seaweed blended with starch and cellulose along with plasticizer and their application.

Fig.1. Global plastic production (1950 - 2020)


Data taken from https://www.statista.com
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II. SEAWEED
Seaweeds are macroalgae that generally live attached to rock or any other substrate in the coastal areas.
Seaweeds are abundantly available, able to grow in a wide range of environments, cost effective, No fertilizer
and pesticides required and easy to cultivate. Seaweed has high biomass and is rich in Polysaccharides,
Agarose, ulvan and fucoidal [2][37]. The seaweed derived hydrocolloids have a diverse application as a
biopolymer in Bioplastic synthesis such as alginate, Agar and Carrageenan [3]. Polysaccharides are Polymers
that have gained a high level interest in the packing industry. Polysaccharides contain Agar, Alginate and
Carrageenan extracted from many species of Red seaweed [49].
Carrageenans are linear sulfated polysaccharides extracted from edible red Seaweeds, it has three main classes:
Kappa(k) forms strong, rigid gel in the presence of potassium ions and due to this property it is used in the
formation of transparent film. Iota(l) forms soft gel in the presence of calcium ions. Lambda(λ) does not form
gel and it is used to thicken dairy products.And Carrageenan extracted from many species of Red seaweed
[32][49].
Agar is a phycocolloid extracted from the cell wall of a group of red algae including Gelidium and Gracilaria.
Agar is used as a thickening and gelling agent while synthesising the Bioplastic. Agar is soluble in hot water and
insoluble in cold water. Agar provides resistance to pathogens. Agar has a. Agar does not require any additional
aids like potassium or calcium for gel formation [34].
Alginates are abundantly present in brown algae like Laminaria japonica and Laminaria digitata. Alginate is
extracted by aqueous alkali solution treatment with NaOH, then the extract is filtered with sodium alginate
powder which is soluble only in water. Calcium alginate is insoluble in water and organic solution hence Ca2+ is
removed. Then obtained alginate can be used in various other applications [34].
Starch is also a natural biopolymer material extracted from plants like wheat, corn, sweet potato, barley. Starch
can be casted into films but the physical and mechanical properties are poor when compared to other
polysaccharides. Improvement of starch based films properties can be made by blending with synthetic
polymer to produce biodegradable materials, mixing with other natural polymers or plasticizers. Several
studies about starch - Carrageenan blended film to enhance the film properties have been done. Blending of
starch with Kappa-carrageenan in the formation of an edible coating increases the mechanical properties of the
film [17].
Cellulose is the most abundant natural polymer derived from wood pulp or cotton linters. Cellulose is difficult
to use in packing because it is hydrophilic and crystalline in nature with poor mechanical properties in its raw
form hence it must be treated with different chemicals like NaOH, H 2SO4 etc. Cellulose can be used as a
compatible polymer with Seaweed [12].
Seaweed cultivation:
Seaweed farming has high economic value for the community's economic development. Seaweed cultivation is
relatively easy for the farmers [28]. Controlled seaweed cultivation allows for high traceability, biomass
composition and properties, high quality, and sustainability. Sustainability of the cultivation is further
increased when the cultivation of seaweed is carried out in Integrated Multi-Trophic Aquaculture (IMTA)
systems. This system incorporated waste produced from one seaweed as a diet of another seaweed. Seaweed
will remove the excess nutrients from the surrounding environment and help in the reduction of CO 2, high
productivity, no risk of potential deforestation, no freshwater consumption, and no pesticides or fertilizers are
used [26][33]. Seaweed cultivation can be enhanced by artificially increasing the ocean nutrients by supplying
nutrient-rich water via upwelling, discharging the secondary sewage, and fish farming water. and Passive
pumping of nutrient-rich water to the surface, to support the naturally floating seaweed beds. These
technologies have both positive and negative impacts on the environment [7][25]. The global annual
production of Seaweeds didn't stop growing and reached 31.2 million tons in 2016 [40].
III. PLASTICIZERS AND COMPATIBILIZERS
Plasticizers are bulky organic molecules, which are mixed with Biopolymers to improve their flexibility and
processability. The efficiency of a plasticizer is related to its ability to make the target material soft and Flexible.

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Glycerol is the most used plasticizer in bioplastic film production using seaweed and other Biopolymers.
Glycerol improved the degradation process, increased flexibility and extensibility, and also improved the
elongation property of the synthesised film[15]. Compatibilizers consist of two parts: one is compatible with
one polymer and the other part is compatible with the other target polymer, and helps in binding of two
polymers. The compatibilizers improved the mechanical strength of heterogeneous biopolymer blend
Bioplastic. For different kinds of blends,various compatibilizers are used. The below Table.1. Shows different
types of plasticizers and compatibilizers and also their purpose of usage [13][42].
Table.1. Plasticizers and Compatibilizers

Plasticizers and Compatibilizers Chemical formula Purpose of usage

Glycerol C3H8O3 Plasticizer


Octanoic Acid C8H16O2 Plasticizer
1.4-butanediol C4H10O2 Plasticizer
EG C2H6O2 Plasticizer
MA C4H2O3 Compatibilizer and grafting
Plasticizer
PE-g-MA Compatibilizer
KPS K2S2O8 Compatibilizer
initiator
DMSO (CH3)2SO Compatibilizer
Initiator
IV. EXTRACTION OF BIOPOLYMER
Seaweeds are collected at the beach, the collected seaweeds are cleaned with fresh water several times to
remove unwanted debris and sand particles. Then Seaweed is dried in the shade. Then the dried seaweed
specimens are subjected to side reduction and then stored in a air tight bags with silica gels [10].
Alkaline treatment extraction(AEA):
This method is carried out by treating the dried seaweed with Alkaline solution (500mL of 5%NaOH) for 2hrs
at 80°C , then the treated sample is rinsed properly and placed in deionised water at room temperature. The pH
of the sample maintained from 6.5-7.5. Then the sample is treated at 120°C for 2hrs. Then the sample is filtered
and cooled at room temperature and frozen overnight to concentrate the agar gel. The frozen solidified agar is
thawed and dried at 50°C for 24hrs.
Photo bleaching extraction(PBA):
The initial method is similar to alkaline treatment with an additional photo bleaching process, the Seaweed
samples are soaked in distilled water and left overnight under the fluorescent lamp prior to photo bleaching
process for 8hrs, Then the concentrated process follows the alkaline treatment extraction method [29].
Carrageenan is extracted from seaweed, firstly the collected seaweed is soaked and then processed through an
alkaline treatment. The extraction process is performed at 60-65°C for 2 hours in 8% KOH solution. The
seaweed and KOH solution ratio in the extraction tank is 1:6. The alkali treated seaweed is rinsed with tap
water till its pH reaches neutral.
The second extraction process is performed at 80-85°C for 2 hours with seaweed and water ratio 1:20 by
adding 3% of celite. The extract is then filtered using a filter press. The concentrated extract is precipitated with
isopropyl alcohol. It is filtered and then dried in the sun for a couple of days. Then the dried carrageenan is
turned into powder using a hammer mill [17].
a)Alcohol precipitation method can be used for all types of Carrageenans however, gel method can only be used
for kappa carrageenan. b)There are mainly two different ways of recovering alginate: the first one is to add acid

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which causes alginic acid to form. The second way of recovering the sodium alginate is by adding calcium salt.
c)Alkaline treatment during the extraction process of agar increases the gel strength from 72g/cm.sq -
1064g/cm.sq. The extraction process of a, b, and c shown in fig.2.[4].

(a) (b)

(c)
Fig.2. Flow chart shows the extraction process of (a) refined Carrageenan;(b) agar; (c) Sodium alginate

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V. FILM PREPARATION
Bioplastic films are prepared by Film casting method. The AEA and PBA extracted from red seaweed G.
salicornia are used as raw material for the formation of Bioplastic film. Sago starch and plasticizer glycerol are
incorporated into the solution to increase work ability [55]. Sago starch (6.8g) is gelatinised and homogenized
in 240mL distilled water using an overhead stirrer in water bath +90°C. Agar powder is then added to the
starch solution, glycerol is mixed to the film forming solution and stirred for 5 minutes, then the film solution is
casted on petridish dried at 50°C overnight [5][29][35].
The 3g of solid matter (Starch and carrageenan blends) is dispersed for every 100mL of distilled water and a
solution of Glycerol is added. The resulting mixture is gelatinised at 68-70°C for 15-20 minutes with continuous
stirring until the starch is completely dissolved. Starch and carrageenan blends are varied at a different ratio.
Air bubbles from the solution are removed using a vacuum oven. The gelatinised mixture is poured on to a non-
sticky mould and kept in a drying oven for 24hours at a controlled temperature of 50°C [1][8].
Arrowroot starch is blended with Carrageenan by different ratios, and a mix of Kappa and iota Carrageenan
(1:1) with concentration of 1.5% using glycerol as a plasticizer. Starch and mixed Carrageenan are mixed in 100
mL distilled water, then the mixture is casted on a flat and levelled glass plate then the plates are held at room
temperature 36-37°C for 24 h [17][53].
Carrageenan is added and glycerol is used as a plasticizer which is hydrophilic in nature. Cellulose is also added
as a copolymer which increases the mechanical property of the film and also acts as water repel barrier since it
is hydrophobic in nature. Cellulose, seaweed and Glycerol are mixed together by continuous stirring and
heating. The solution is subsequently degassed to remove the air bubbles under vacuum, then the solution is
casted on the petri dish of a teflon plate and kept at room temperature until it is dried [4][20].
After drying the biofilms are removed from the mould/teflon sheet/petri dish and then the Biofilm tensile
strength, elongation, solubility, and chemical properties are studied.
VI. CHARACTERISTICS OF BIOPLASTIC
Fourier Transform Infrared (FTIR) Spectroscopy:
FTIR uses the mathematical process to translate the raw data into the actual spectrum. FTIR identifies the
presence of Organic and Inorganic compounds in the sample [43].
FTIR absorbance bands of AEA and PBA Bioplastic films contribute to complex vibrational stretches due to
intra, inter and free molecular hydroxyl groups. The FTIR spectra with low absorbance band of similar
components might be due to the intense interaction to the material. More intense chemical interaction is
feasible, as this indicates a better entanglement between Agar, Sago starch and glycerol. The chemical
interaction is found stronger in PBA bioplastic film than compared to AEA bioplastic film [29].
Starch/carrageenan blended films have a smooth surface at room temperature. Carrageenan contributes to the
formation of a rigid network making the film less hygroscopic. Viscosity of the solution increases with increase
in the amount of carrageenan. The films synthesised with only starch shows the wrinkled surface. The IR
analysis showed C-O-C bond and C-H bond in the film. It also suggests that the cause for physical
entanglements is due to the existence of hydrogen bonds. The films with high Carrageenan concentration show
a high rigid network and hydrogen bond [8].
Arrowroot starch consists of high starch and amylose contents. The amylose content leads to formation of
strong polymeric matrices. This starch exhibited a monomodal distribution. The arrowroot starch exhibited
several bands characteristic in FTIR spectra. The film synthesised by blending Arrowroot starch and
carrageenan has good mechanical strength [14].
FTIR analysis is regarded as the reliable and cost effective analytical tool to identify the polymers, functional
group, and bonding within the films the spectra of seaweed and seaweed/cellulose composite film and their
functional group are studied. The intensity of O-H band absorbance increased due to the formation of hydrogen
bonding between -OH groups from the seaweed and cellulose within the polymer matrix as also with the
addition of crystalline nano cellulose into alginate film matrix [23].

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Scanning Electron Microscope (SEM):
SEM is a technique used for visualization of surfaces. By this we can know the morphological and structural
characterization of biofilms [30]. The air bubbles trapped in the matrix of AEA and PBA Bioplastic film made the
film less dense and non homogenous. The continuous phase is found that the added glycerol is successfully
incorporated in the polysaccharide chain and disrupted intermolecular hydrogen bonds. Air bubbles weaken
the mechanical property of the Biofilm [29].
The strength of the biofilm depends on the structure of the polymer and the role of blend and composites in
manipulating properties. starch/carrageenan matrices increase the biofilm strength. Tensile strength of the
film is comparatively more when the carrageenan concentration is more than the starch concentration [50].
Arrowroot starch and carrageenan film as good tensile strength. The excess starch concentration loses the
bond between carrageenan. The strength of the biofilm can be explained in terms of polymer matrices; The
tensile strength values are directly related to the increase in the degree of crystallinity of the polymer matrices.
Arrowroot starch increases the strength of the biofilm [17].
Cellulose and carrageenan blended the biofilm exhibit good strength. The Cellulose Nano Crystal (CNC) with
k.Carrageenan(KC) matrix exhibits a reinforcing effect. In the biofilm the tensile strength increases. In the
biofilm with increase in CNC concentration. In the biofilm, incorporating CNC into the KC matrix results in
powerful interaction between the matrix and the filler and promotes mechanical strength and rigidity [11].
Thermogravimetric Analysis(TGA):
Thermogravimetric analysis or thermal gravimetric analysis is a method of thermal analysis in which changes
in physical and chemical properties of materials are being observed as a result of increase in temperature [24].
TGA analysis is conducted to determine the effects of thermal stability of bioplastic film. Both of the bioplastic
film AEA and PBA experienced weight loss due to evaporation of moisture content of the bioplastic film and
these are all glycerol. Glycerol decomposes at temperature 260°C whereas the thermal decomposition of agar
and starch are at temperature 300°C. AEA bioplastic film showed higher thermal stability than compared to
PBA bioplastic.Thermal stability of bioplastic film depends on many factors like the ability of the molecule to
discharge cation and networked structure of molecules. Higher degree of cross-linking in a certain composite
contributed to stronger thermal stability [29].
Analysis of the thermal property starch/carrageenan is determined by heating at room temperature upto 900°C
with the heating rate of 10°C per minute. The breakage of starch bonds happens between 200 to 360°C. The
addition of starch along with the carrageenan in the film formation gives good thermal stability [41].
The arrowroot starch/carrageenan based biofilm has good strength and thermal stability. Incorporating starch
into the carrageenan matrices gives good thermal resistance capacity. The breakage of starch bonds occurs
between 121 to 170°C [16].
The biofilm formed by blending Cellulose and carrageenan exhibit good thermal resistance since the CNCs are
moisture bonded on the Seaweed surface. CNCs tend to rearrange the molecular structure by removing the
amorphous region, hence the CNCs show highest thermal stability. The impurities in seaweed matrices can
initiate the heating processes because they have more active sites than CNCs [19].
Water solubility:
The solubility of the film is determined by a water solubility test. The solubility of the film is expressed in
percentage. The difference between the initial weight and final weight after soaking and drying are noted. The
solubility (S%) is calculated from the following equation
(S%) = [(W1-W2)/W1]*100
W1 - initial weight of the film
W2 - final weight of the film after soaking in water and drying in the oven
S% - solubility of the film.

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The solubility of the Starch/carrageenan film ranges between 16-23%. The solubility increases with an increase
in starch concentration, while the plasticizers have no effect on the solubility of the film. Starch has more
hydroxyls and these hydroxyls interact with water making the Bioplastic more soluble [39].
Film solubility in water is an essential property in selecting suitable food packing bioplastic. For food
application, a film with good water insolubility is required. The water solubility of the film synthesized with
arrowroot starch and carrageenan is suitable for food packing. Solubility of the film reduces with an increase in
arrowroot starch concentration to some extent, if the arrowroot starch concentration is increased beyond the
necessity the filler becomes too dense and causes the bonds of carrageenan to become weaker [17]
The Water solubility of neat seaweed film is very high which is probably due to the hydrophilic nature of
seaweed. The Cellulose particle indicated a strong hydrogen bond formation between the hydroxyl group with
hydroxyl groups in the seaweed film matrix resulting in the enhanced stability of seaweed film in water [23]
Biodegradability by soil burial test:
Biodegradability is known as the ability of polymers to undergo structural alteration and scission of polymeric
chains that are affected by environmental factors and micro-organism activities.
AEA and PBA bioplastic film buried in different types of soil condition. The percentage of weight loss of PBA
film is lower than AEA bioplastic film, this might be due to the packed structure of the film, more the air bubbles
less gel structure of polymatrix of AEA bioplastic film increase the water absorption capacity and promoted the
growth of microorganism [29]
Biodegradability test is conducted of both indoor and outdoor microorganisms from the soil that react to the
water within the biofilm and start decomposing due to breakdown of the polymer chain in the biofilm. The
reaction is slow for pure carrageenan biofilm after the first week but a sudden rise in the second week due to
the biofilm matrix being held together more stronger than whole seaweed biofilm [18].
The Starch- carrageenan biofilm degradation occurred after 10days of exposure in soil. The film is degraded
easily since organic polymer is usually prone to microorganism attack, the starch will increase the filler loading.
Films filled with inorganic material appear to slow down the rate of degradation due to strong interaction
between filler and matrix. When comparing the seaweed based film with the conventional mulch film made of
PLA, the conventional mulch film showed the lowest weight loss [21].
The addition of hydrophilic starch and glycerol in the composition of film improves the water absorption
capacity and hence increases the water activity of the film and promotes the growth of the microorganisms.
Glycerol from the composite film passes through the cell membrane and is metabolized by the microorganism
and also enhances the weight loss of bioplastic film. If the soil is dry the less microbial activity is observed and it
reduces the degradability rate.
VII. APPLICATIONS
The global biodegradable plastic market accounts for less than 1% of the overall plastic market, it is expected to
grow at a fast pace over the next upcoming years [27]. Biodegradable plastics have found their end-use in a
variety of commercial applications like Bags and toys packing in commercial sector; agricultural foils,
horticulture and nursery products in agriculture industry ;facemask and washing powder packing materials in
cosmetic industry and toiletry industry; drinking cups, overwarp, straws containers and edible films in food
packing industry; capsule coating in pharmaceutical industry. The Table. 2. Shows the application of seaweed
base composites [52].
Table.2. Application of seaweed based composites in food packing and coatings

Types of composites Application

Alginate/nanocrystalline cellulose Polymeric packing films for food

Alginate/starch Packing of pre cooked ground beef patties

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carrageenan/locust bean gum/nano clay shelf life extinction of food

Alginate/cinnamon essential oils edible film for food, quality retention of fresh cut pineapples

K.Carrageenan/zataria multiflora essential oil antimicrobial packing for food

Agar/nanocrystalline cellulose/savory active packing for improving safety and


Essential oil shelf life of food stuff.

Carrageenan/glycerol packing for instant noodles, flavouring, coffee mix, candy


wrappers and others

K.Carrageenan sachet, interleaf for frozen foods.

VIII. CONCLUSION
Bioplastic can be an alternative source for petroleum based plastic. Bioplastic synthesised from seaweed/
starch/ cellulose and other composites has quite good thermal stability, water solubility to some extent, but
has a good degradation rate. Since plastic pollution is increasing day by day we can enumerate the use of plastic
by this Seaweed based plastic as it is renewable and Eco-friendly in nature.
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