Accepted Manuscript

Title: Extraction of nano cellulose fibers from the banana peel

and bract for production of acetyl and lauroyl cellulose

Authors: K. Harini, K. Ramya, M. Sukumar

PII: S0144-8617(18)30990-1
DOI: https://doi.org/10.1016/j.carbpol.2018.08.081
Reference: CARP 13978

To appear in:

Received date: 4-6-2018

Revised date: 25-7-2018
Accepted date: 19-8-2018

Please cite this article as: Harini K, Ramya K, Sukumar M, Extraction of nano cellulose
fibers from the banana peel and bract for production of acetyl and lauroyl cellulose,
Carbohydrate Polymers (2018), https://doi.org/10.1016/j.carbpol.2018.08.081

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Extraction of nano cellulose fibers from the banana peel and bract for production of acetyl

and lauroyl cellulose

K. Harini1, K. Ramya2, M. Sukumar1*

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Centre for Food Technology, Anna University, Sardar Patel Road, Guindy, Chennai,

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Tamilnadu, India.

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The Bannari Amman Institute of Technology, Sathyamangalam, Erode District, Tamil Nadu,
India.

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* Corresponding Author (s):
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1. Name: Dr. M. Sukumar.
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Designation: Professor
Address: Centre for Food Technology, Anna University, Chennai, Tamilnadu, India.
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Phone Number: +91-9444309138.

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E-mail ID: sukumarcbt@gmail.com; sukumar@annauniv.edu.

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Graphical abstract
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Highlights:

 The microwave digestion method was analyzed to be effective in the extraction of MCF.
 NCF’s were extracted by balling milling assisted ultra-sonication method.
 NCF’s of banana peel and bracts were found to possess high thermal stability.
 NCF’s of banana peel and bracts were examined to be type I cellulose.
 NCF’s were found to be a good source for the production of cellulose based polymers.

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Abstract

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The principal aim of the present study is to develop a method for the production of cellulose

nanofibers, from the banana peel (BP) and bract (BB). It is also the aim of this study to produce

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cellulose-based biopolymers through acetyl and lauroyl modifications. The microwave digestion
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method and ball milling assisted ultra-sonication method was optimized for sustainable
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extraction of micro and nano cellulose fibers, respectively. The microwave digestion method was
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found to be effective in the removal of hemicellulose and lignin. Micro and nano cellulose fibers

of BP and BB were found to contain type I cellulose structure. Thermal stability and crystallinity
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index of cellulose nanofibers were examined to be higher than it’s native micro cellulose. Nano
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cellulose fibers were examined to be a potential source for production of acetyl and lauroyl
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cellulose, with a high degree of substitution and thermal stability. Hence, microwave digestion

and ball milling assisted ultra-sonication method was proven to be effective in the extraction of
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nano cellulose fiber for development of cellulose-based polymers.

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Abbreviations: BP – Banana peel; BB – Banana bract; CA – Cellulose acetate; CL – Cellulose

laurate.

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Keywords: Micro cellulose fiber; Nano cellulose fibers; Ball milling; Ultra-sonication; Acetyl

cellulose; Lauroyl cellulose.

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1 Introduction

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Current major threats to society are the aggregation of non-biodegradable polymers and over-

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utilization of fossil resources (Deng, Huang, Zhou, Chen, & Fu, 2016). Fossil resources are being

utilized for energy and polymer production for many decades. This is one of the reasons for

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depleting fossil resources. The main global concern has always been the rising environmental
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pollution, due to improper recycling techniques and non-biodegradability of petroleum-based
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polymers. Among the above-cited causes, non-biodegradable nature of polymers is the primary
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reason, for the alarming threat to the environment. Proper use of natural polymers can be the
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remedy for this red alert environmental problem. Thus, there is a growing interest among
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researchers, to develop biodegradable materials for substitution of petroleum-based polymers

(Shaikh, Pandare, Nair, & Varma, 2009).

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Cellulose is the most abundant polysaccharide in the world and it is widely considered to be a
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long-term renewable alternative to synthetic plastics. Cellulose is a long chain linear

homopolymer comprising anhydro-β-D-glucopyranose units linked by (1→4) glycosidic bonds

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(Kono, Erata, & Takai, 2003; Nishino, Matsuda, & Hirao, 2004; Spinella et al., 2016; Wada,

Nishiyama, & Langan, 2006; Yadav, Saini, & Maji, 2017; Zhang, Karimkhani, Makowski,

Samaranayake, & Rowan, 2017). All the plant materials are rich in cellulose, consequently, it

provides the incomparable renewable natural resource. Cellulose is the natural biopolymer,

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having a microfibril structure of both amorphous and crystalline regions. Cellulose has a wide

range of applications compared to other natural polysaccharides such as starch and proteins. It is

difficult to produce flexible polymeric materials from native cellulose. Therefore, many

researchers have worked on conversion of complex cellulose molecules, to simple cellulose

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nanofibers or cellulose nanocrystals (Cai, Kimura, Wada, & Kuga, 2009; Y. Chen, Wu, Huang,

Huang, & Ai, 2015; Kedzior, Dubé, & Cranston, 2017; Liu, Li, Xie, & Deng, 2017). Agro-

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industrial wastes are lignocellulosic materials, which is a composite of cellulose and lignin

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adhered by the hemicellulose (Huang, Liu, Sun, & Shang, 2017). Chemical treatment methods

have been examined to be successful in the production of cellulose nanofibers from agro-wastes.

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These chemical treatment methods involve alkali treatment for removal of impurities and acid

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hydrolysis for disruption of amorphous regions in cellulose fibers. The corrosive chemicals used
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in traditional chemical treatment methods are hard to handle. Therefore, these methods are not
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sustainable for the production of cellulose nanofibers (Yadav et al., 2017). The microwave

treatment is one of the modern methods to catalyze any reaction (Huang et al., 2017). Therefore,
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this method has been adopted in this study to facilitate isolation of cellulose by aqueous
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extraction of impurities. Electromagnetic microwaves disrupt the linkages in dipolar water

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molecules to release high amounts of localized heat energy (Bu & Guo, 1997). This localized

heating may disrupt the hemicellulose and lignin present in the lignocellulose. Consecutively, it
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may also facilitate the penetration of water molecules for removal of impurities from cellulose.

Alkali or oxidative pretreatments are not used in microwave digestion method. Therefore,
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cellulose microfibers produced from microwave digestion method may retain the innate chemical

nature of cellulose, compared to traditional chemical extraction methods. Ball milling is one of

the modern methods for particle size reduction of cellulose fibers. But this method is not suitable

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for localized removal of amorphous regions in cellulose. Therefore, most of the reports on ball

milling production of nano cellulose, utilize the acidic medium to facilitate the removal of

amorphous regions (Nuruddin, Hosur, Uddin, Baah, & Jeelani, 2016; Rahimi Kord Sofla, Brown,

Tsuzuki, & Rainey, 2016). Optimized ultrasonic treatment of micro cellulose fibers can facilitate

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the removal of amorphous regions in the axial direction through cavitation (Yadav et al., 2017).

The proposed method of cellulose nanofiber production combines the ball milling and

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ultrasonication, to focus on mechanical disruption of amorphous regions in micro cellulose

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without chemical treatment. There is no involvement of an acidic environment in the ball milling

assisted ultrasonication method. As a result, cellulose nanofibers may inherit its native chemical,

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thermal and crystalline properties. Cellulose nanofibers are sensitive to any kind of

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modifications, because of its reduced size and improved surface area. Therefore, it can be
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utilized for the wide range of applications (Cai et al., 2009; Kedzior et al., 2017). The banana is
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one of the fruit crops, majorly cultivated all over the world. Every part of the banana is useful,

and they are also rich in cellulose (Tibolla, Pelissari, & Menegalli, 2014). Banana processing
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industries releases tons of banana peels, flower bracts, and saps as waste materials. These waste
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materials can serve as a potential source of cellulose nanofibers (Tibolla, Pelissari, Martins,
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Vicente, & Menegalli, 2018; Tibolla et al., 2014).

Chemical modification of cellulose is an effective way to overcome the difficulties in the wide
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range application of cellulose (Candido & Gonçalves, 2016). Esterification (Q. L. Lu, Li, Tang,
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Lu, & Huang, 2015), silylation (Lu, Askeland, & Drzal, 2008), carbonylation (Leung et al.,

2011), etherification (Hasani, Cranston, Westman, & Gray, 2008) and grafting (He et al., 2015)

are few modifications, that can be employed in cellulose for target specific applications. Acetyl

cellulose is one of the most important cellulose derivatives, because of its wide applications in

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production of membranes (Ragab et al., 2014), films (Gutierrez et al., 2017), fibers (Chen, Xu,

Wang, Cao, & Sun, 2016), plastics (Tedeschi et al., 2018), filters (Czayka & Fisch, 2012), etc.

Candido & Gonçalves (2016) reported that the worldwide market of cellulose acetate is projected

to be about 1.05 million metric tons and its estimated price is around $1.80/lb. Cellulose acetate

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is produced from acetylation of hydroxyl groups present in anhydroglucose units (AGUs) of

cellulose. Acetylation of cellulose can be carried out in the presence of acetic acid as a solvent

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and concentrated sulfuric acid as a catalyst (Kono, Hashimoto, & Shimizu, 2015). Fatty acid

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esterification also plays a major role in the modification of cellulose. Many researchers have

worked on fatty acid esterification of cellulose (Ratanakamnuan, Manorom, & Inthasai, 2013;

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Singh, Sharma, & Singh, 2014). Singh et al. (2014) reported that stable mechanical and

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biodegradable properties can be incorporated in cellulose by esterification of dodecanoic acid.
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The main aim of this study is the synthesis and characterization of cellulose nanofibers from
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banana peel and bract. Moreover, it is also the aim of this study to modify the nano cellulose
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fibers, by acetylation and esterification for production of acetyl and lauroyl cellulose,
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respectively. Morphology, particle size, thermal stability, and crystallinity of micro and nano

cellulose fibers were characterized to prove the efficiency of microwave and ball milling assisted
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ultrasonication method. Moreover, the degree of substitution and thermal stability of modified

cellulose derivatives were examined to prove its thermoplastic properties.

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2. Materials and Methods

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This work was done in four parts, First: Dried powders of banana peel and bract were subjected

to Soxhlet extraction for removal of polar and nonpolar extractives. Second: Residual powders of

banana peel and bract were subjected to microwave digestion method for production of micro

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cellulose fibers. Third: Micro cellulose fibers produced from banana peel and bract were treated

with ball milling and sonication for sustainable production of nano cellulose fibers. Fourth: Nano

cellulose fibers were modified using acetylation and esterification to give acetyl and lauroyl

cellulose, respectively. Fig. 1, illustrates the general schema of the study.

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Fig. 1: General schematic diagram of the study [MCF – Micro cellulose fibers; NCF: Nano
cellulose fibers]

2.1 Raw materials

Banana peel and bract were collected from local vegetable vendors in Chennai, Tamilnadu,

India. The samples were dried in a fluidized bed dryer at 50 ℃ and milled to dry powder. These

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powders were subjected to Soxhlet extraction with acetone and hexane for 10 h each, to remove

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unwanted polar and non-polar compounds. The extracted lignocellulose powder was dried at

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room temperature to remove residual solvents present in the sample. All the analyses chemicals

were purchased from local suppliers of Merck Millipore (Merck Specialities Pvt. Ltd.). Purity:

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EMPARTAACS grade for analysis.

2.2 Isolation of micro cellulose fibers

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Microwave assisted extraction of cellulose has been already reported by Hartati, Kholisoh,

Kurniasari, & Riwayati (2016). They have used chemicals like acetic acid for the extraction of
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cellulose. Deionized water was only used in this study for microwave cellulose extraction, to
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avoid chemical treatments. We have optimized the solid solvent ratio and power range for the

removal of soluble impurities from cellulose (Table S1). The time required for microwave
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digestion was not optimized because it will vary according to sample composition. Therefore, the
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microwave digestion time depends on the number of cycles required for the removal of

impurities from cellulose. 10 g of dried pre-treated powder was mixed with 90 mL of deionized
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water and subjected to microwave (Whirlpool Corporation, US) digestion at 525 W, for 5 min.

Then the mixture was stirred at 600 rpm for 30 min and filtered to remove the unwanted

dissolved molecules. The filtered cake containing insoluble cellulose molecules was subjected to

microwave treatment again. This process was continued until the complete removal of unwanted

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impurities from cellulose. After completion of microwave digestion, 5% (v/v) H2O2 was added to

the reaction mixture (incubated at 70 ℃ for 30 min) to facilitate the bleaching of micro cellulose

samples. Bleached micro cellulose fibers were freeze-dried and stored in polyethylene bags until

further use.

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2.3 Conversion of micro cellulose fibers to cellulose nanofibers

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Initially, the treatment conditions for ball milling and ultra-sonication were optimized using the

central composite design analysis. Transmission electron microscope and DLS analysis results of

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cellulose fibers were taken as responses. Design parameters and corresponding responses were

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tabulated in Table S2-S5. Optimized parameters were used for the production of nano cellulose

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fibers. 25 g of micro cellulose fibers extracted from agro waste was suspended and soaked in 200
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mL of DMSO solution for 24 h. Then the mixture was milled in Spex 8000M high-energy ball
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milling machine for 2 h with 440C hardened steel balls (1/4 inch in diameter). The weight ratio

of powder to the ball was set at 1:10. The milled micro cellulose-DMSO solution was subjected
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to Ultra-sonication (Qsonica Q700, Cole-Parmer, USA) at 200 W (20 kHz) power output for 1 h,
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with 10 min intervals for every 15 min.

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2.4 Conversion of nano cellulose fibers to cellulose acetate (CA)

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Cellulose acetate was prepared using the method described by Candido & Gonçalves (2016). 24

mL of glacial acetic acid was added to 10 g of nano cellulose fiber, and this mix was stirred at 37
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℃ for 1 h. Subsequently, 40 mL of glacial acetic acid and 0.08 mL of H2SO4 was added to the

mixture, which was stirred for 45 min at 1000 rpm. After that, the mixture was cooled to 18 ℃,

and it was added to 28 mL of acetic anhydride and 0.6 mL of H2SO4. Then, the mixture was

stirred for 1.5 h at an elevated temperature of 35 ℃. Then, a solution containing 10.0 mL of water

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and 20 mL of glacial acetic acid was added dropwise over the reaction mixture for 1 h under

stirring. Finally, the material obtained was washed with distilled water until pH 7.0.

2.5 Conversion of nano cellulose fibers to cellulose laurate (CL)

Cellulose laurate was prepared using the method described by Singh et al. (2014), with few

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modifications. 3 g nano cellulose fibers were mixed with 20 mL of DMAc and stirred at 700 rpm

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(50 ℃) for about 8 h. The reaction was carried out in a flat-bottom flask equipped with the

magnetic stirrer and condenser. The mixture was continuously stirred at 80 ℃, with the addition

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of 1.8 g LiCl, until it became a homogeneous transparent solution. Lauroyl chloride and DMAP

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were added to the reaction mixture at 10 mmol concentration, the stirring was continued for 6h at

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80 ℃. Special care was taken to control the temperature under 80 ℃, throughout the reaction, to
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avoid charring of cellulose. After completion of the reaction, the mixture was poured with cold
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distilled water to precipitate the product and was successively washed with ethanol. Washed

cellulose laurate was freeze-dried to remove solvents.

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2.6 Yield calculations

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The yield of micro cellulose fibers was calculated by dividing the weight of micro cellulose
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fibers with initial sample powder weight (obtained after extracting polar and nonpolar fractions).
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The yield of nano cellulose fibers was calculated by dividing the weight of nano cellulose fibers

with the weight of micro cellulose fibers. The yield of crude cellulose acetate (CA) and laurate
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(CL) was calculated by acetone and chloroform dissolution methods, respectively. Cellulose

acetate samples were subjected to dissolution with acetone for 5 hours in a magnetic stirrer

rotating at 600 rpm. The resultant solution containing dissolved CA was separated from

undissolved cellulose molecules (settled at the bottom). This separation process was repeated 5

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times to separate the maximum amount of CA from the samples. The extracted solutions were

freeze-dried to remove the solvent from cellulose acetate. The same procedure was followed for

extraction of CL, using chloroform as a solvent. The yield of CA and CL was calculated by

dividing the weight of CA or CL with the weight of nano cellulose fibers. All the yields were

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represented in percentage.

2.7 Characterization

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2.7.1 Chemical composition of micro and nano cellulose fibers

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Lignin content of the samples was determined using TAPPI standard method T 222 Om-88

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(1999), using 72 % (w/w) sulfuric acid. Hemicellulose estimation was conducted using sodium
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hydroxide dissolution method described by Morais, Rosa, & Marconcini (2010). Ash content
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was estimated using the muffle furnace treatment. The cellulose content was estimated through
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the method described by Updegraff (1969).

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2.7.2 Scanning electron microscopic analysis. The surface micrographs of micro and nano
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cellulose fibers were obtained through the scanning electron microscopic analysis (TESCAN

VEGA3, Czech Republic), performed according to the method described in our previous work
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(Harini, Chandra Mohan, Ramya, Karthikeyan, & Sukumar, 2018). The images were taken at an
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accelerating potential of 15 kV in different magnifications.

2.7.3 Transmission electron microscopic analysis. The TEM technique was used to prove the
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efficiency of the source and method used to obtain the nano cellulose fibers. For the analyses,

each suspension was placed under ultrasound for 5 min; then, a drop of the suspension was

placed on a carbon microgrid (300 mesh) and dried at 60 ℃ for 20 min. Transmission electron

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micrographs were obtained using TECNAI’10 transmission electron microscope (Koninklijke

Philips N.V., Amsterdam, Netherland), operating at an accelerating voltage of 75 kV.

2.7.4 Particle size analysis. Particle size distribution of micro and nano cellulose fibers was

measured using laser diffraction system (HELOS-BR, Sympatec Inc., Princeton, NJ, USA),

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operating as stated in our previous work (Chandra Mohan et al., 2016).

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2.7.5 Thermal analysis. TG-DSC analyses were performed, according to the method described in

our previous works (Harini et al., 2018; Sudharsan et al., 2016), using NETZSCH STA 449F3

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(NETZSCH-Gerätebau GmbH, Germany) instrument.

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2.7.6 X-ray diffraction analysis. Wide angle X-ray diffraction measurements were carried out in
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D8 Advance Bruker AXS X-ray powder diffraction instrument using a one-dimensional Debye–
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Scherr camera, Cu Ka radiation (wavelength 0.1542 nm) operates at 40 kV and 35 mA. The
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diffraction pattern was recorded in 2θ ranging from 10 - 70º, with scan interval and the rate of

0.04 and 1º/min, respectively. The crystallinity index (CI) was calculated using the method
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described by Acharya, Hu, Moussa, & Abidi (2017), with equation (1). The crystalline and
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amorphous peaks were deconvoluted (using a Peakfit Gaussian function) to estimate the area
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under the peak of crystalline (Icry) and amorphous regions (Iam).

𝐼𝑐𝑟𝑦
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𝐶𝐼(%) = 𝐼 × 100% Eq. (1)

𝑡𝑜𝑡𝑎𝑙

Where, Itotal – Total area under XRD peaks [Itotal = Icry + Iam]
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2.7.7 1H and 13C Nuclear magnetic resonance analysis. NMR experiments were performed on a

Bruker AVIII 400 spectrometer, equipped with a 5 mm PABBO BB/19F-1H/D Z-GRD

Z136881/0003 probe (Bruker Bio-Spin GmbH, Germany), operating at 400.23 MHz for 1H

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experiments and 100.65 MHz for 13C experiments. All the spectra were acquired and processed

with Bruker Top Spin version 3.0 on a Windows PC. CA samples (10–20 mg) were dissolved in

600 µL of C3D6O, and CL samples were dissolved in 600 µL of CDCl3. Each solution was

placed in a 5 mm NMR glass tube (Wilmad - Labglass Co., USA). The sample temperature was

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set to 296.9 K (Kono et al., 2015).

2.8 Statistical analyses

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Cellulose extraction and conversions were conducted in triplicates to validate the yields of

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cellulose and converted products. An average parameter value for each process was evaluated

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using the triplicates and they are represented in the form of Mean ± Standard deviation.

3 Results and discussions N

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3.1 Chemical composition, yield, morphology, and particle sizes of micro and nano cellulose
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fibers
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Table S6 tabulates the chemical compositions of raw, micro and nano cellulose fibers of banana
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peel (BP) and banana bract (BB). Raw banana bract powder was examined to have higher
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cellulose content than the banana peel. The cellulose content of banana peel and bract were

found to be higher than 42 % reported for kelp waste (Liu et al., 2017), and 40 % reported for
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sugarcane bagasse (Leão, Miléo, Maia, & Luz, 2017). The microwave digestion of BP and BB

lignocellulose in deionized water produce localized heating, to break cellulose molecules from
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associated hydro dissolving substances. Fig. 2, shows the graphical schematic representation of

microwave digestion process for the production of micro cellulose fibers. The localized heating

not only breaks the impurities from cellulose molecules, it may also aid the water molecules to

occupy the space between the cellulose microfibers. This will, in turn, facilitate the removal of

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non-cellulosic molecules (during washing and filtration step) at the end of each microwave

digestion cycle.

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Fig. 2: Schematic representation of micro cellulose fiber production by microwave

digestion method
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Initially, banana peel and bract lignocellulose powders were subjected to microwave digestion
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treatment for 5 repeated cycles. The resultant samples were analyzed through the scanning

electron microscope to examine the morphology and particle sizes of cellulose molecules. The
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micrographs of samples were illustrated in Fig. S1 and S2, for banana peel and bract,

respectively. Presence of residual impurities in micro cellulose samples of both banana peel and

bract was evident through SEM micrographs. Therefore, samples were further subjected to a

repeated microwave digestion process to improve the efficiency of micro cellulose extraction.

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The cellulose content of both BP and BB micro cellulose fibers were examined to be higher than

raw samples (Table S6). This result proves the efficiency of microwave digestion process in the

removal of lignin and hemicellulose impurities. The extraction yield of micro cellulose fiber

from the residual banana peel and bract powder was estimated to be 55.48 ± 1.57 % (w/w) and

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64.67 ± 2.36 % (w/w), respectively. Fig. 3, depicts the morphology of micro and nano cellulose

fibers extracted from banana peel and bract. Scanning electron micrographs of micro cellulose

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fibers extracted from the banana peel (BPM) showed irregular bundles of cellulose fiber, with

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visual particle size ranging from 30 to 19.2 µm in diameter (values were taken from all analyzed

samples). DLS particle size analysis showed an approximate particle size range of ~520 to 26 µm

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for the BPM sample, with the average particle size of 351 µm (Fig. S3). Scanning electron

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micrographs of micro cellulose fibers extracted from the banana bract (BBM) showed linear
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bundles of crystalline cellulose, with visual particle size ranging from ~45 to 15 µm in diameter
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and ~434 to 272 µm in length (values were taken from all analyzed samples). DLS analysis

revealed the approximate particle size range and average particle size of BBM to be ~743 to 51
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µm, and 431 µm, respectively. The observed morphology of cellulose structures was in
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agreement with other reports (Gong, Li, Xu, Xiang, & Mo, 2017; Li et al., 2015).
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Fig. 3: Scanning electron micrographs of micro [M] & nano cellulose fibers [N] [BP – Banana peel;
BB – Banana Bract; BM – Ball milled]

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Fig. 4 illustrates the schematics for production of cellulose nanofibers, using ball milling and

sonication treatments. The micro cellulose fibers were subjected to soaking in DMSO to

penetrate the loose regions between cellulose fiber bundles, and to make them swell in the radial

direction (Yadav et al., 2017). Swelling of cellulose fibers may increase the efficiency of the ball

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milling process, which can disrupt the loose regions in between cellulose fiber bundles (Chandra

Mohan et al., 2016). The particle size reduced cellulose was subjected to ultra-sonication, which

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is the process of liquid state acoustic cavitation, leading to creation, growth, and rapid collapse of

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microbubbles. Localized hot spots generated in this process renders the creation of shock waves

on the surface of cellulose microfiber, leading to erosion of non-crystalline materials along the

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axial direction, forming nano cellulose fibers (Yadav et al., 2017).

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Fig. 4: Schematic representation of nano cellulose fiber production by ball milling assisted

ultra-sonication method
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Ball milled micro cellulose fibers were recovered and analyzed through the scanning electron

microscope and DLS particle size analyzer, to confirm the particle size reduction of micro
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cellulose fibers. Ball milled micro cellulose fibers of banana peel (BM-BPM) showed visual

particle size ranging from 3.27 to 3.30 µm in diameter. DLS analysis showed the average particle

size of BM-BPM to be 15.42 µm. Ball milled micro cellulose fiber of the banana bract (BM-

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BBM) showed visual particle size ranging from 11.1 to 3.92 µm in diameter. DLS analysis

revealed the average particle size of BM-BBM to be 29.31 µm. These results proved the

efficiency of ball milling in particle size reduction of micro cellulose fibers.

Ball milled micro cellulose fibers were subjected to ultra-sonication treatment to disintegrate

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amorphous regions in between the cellulose fibers. Consequently, particle sizes of cellulose

fibers were reduced to nano range from micro range. Percentage of nanofibers extracted from

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micro cellulose fibers was estimated to be 76.58 ± 1.97 % (w/w) and 74.47 ± 1.23 % (w/w) from

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banana peel and bract, respectively. Scanning electron micrographs and transmission electron

micrographs (Fig. S4) of banana peel nano cellulose fibers (BPN), showed fibrous morphology.

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The diameter of cellulose fibers was found to be within the size range of 100 nm. This proves the
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effectiveness of ball milling assisted ultra-sonication treatment in the production of nano
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cellulose fibers. The visual average diameter of BP and BB nano cellulose fibers was estimated
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to be 73 nm and 89 nm, respectively. DLS analysis showed the particle size range of nano
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cellulose fibers to be between 180 nm and 2300 nm. The average particle size of BPN was
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estimated to be 1285 nm, in DLS analysis. Cellulose nanofibers extracted from the banana bract

also showed linear fibrous morphology. Their particle size was ranging from 240 to 2100 nm,
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with an average particle size of 972 nm (DLS analysis). Scanning electron micrographs showed

significantly reduced particle size than DLS particle size analysis, in all the investigated cellulose
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samples. This observation can be attributed to the linear nature of cellulose fibers. DLS particle
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size measurements mainly depend on the scattering of light from colloidal sphere suspensions.

Therefore, the particle size of linear cellulose fibers cannot be measured through the DLS

method. Similar observations were also noted and explained by Gong et al. (2017).

3.2 Thermal stability of micro cellulose fibers and nano cellulose fibers

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3.2.1 Thermogravimetric analysis

Thermal stability of micro cellulose fibers and nano cellulose fibers was examined by

thermogravimetric and differential scanning calorimetric analysis. Fig. 2, shows the

thermogravimetric weight loss curves of micro and nano cellulose fibers extracted from banana

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peel and bract. An initial weight loss of 9.94 % (w/w), corresponding to moisture loss was noted

for banana peel micro cellulose fibers. Spinella et al. (2016) stated that weight loss up to 150 °C

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is attributed to loss of bound water, which provides a tool to determine the water affinity of nano

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cellulose fibers. Major weight loss of 66.42 % (w/w) was noted between 201 and 214 ℃. This

weight loss may correspond to the disintegration of cellulose molecules through pyrolysis, with

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peak disintegration temperature of 200.7 ℃ (Fig. S5: DTG curve). Cellulose nano fibers
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extracted from banana peel showed a major weight loss of 66.56 % (w/w) between 284 and 368
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℃, with peak disintegration temperature of 346 ℃. Interestingly, this result indicates the increase
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in thermal stability of BP cellulose, on the reduction of its particle size from the micro to nano
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range. Many studies on cellulose nano fiber production reported that there is a reduction of
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thermal stability in nanofibers compared to microfibers (Liu et al., 2017; Oun & Rhim, 2017).

They attributed this thermal stability behavior of nano cellulose fiber to associated chemical
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residues on the surface of cellulose fibers (attached during acid/alkali treatment given for

production of nano cellulose fibers). The increase in thermal stability of nano cellulose fibers,
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noted in this study may be due to lack of acid and alkali treatments in ball milling assisted
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ultrasonication method. This is the major advantage of the proposed process for the production

of nano cellulose fibers. After major weight loss of cellulose disintegration, a steady state of

thermal degradation was noted between 214 and 800 ℃, with the final residual weight of 8.96 %

(w/w). This residue may contain left over carbon molecules and other trace minerals after

19
degradation of cellulose (Rahimi Kord Sofla et al., 2016). The residual weight of 3.26 % (w/w)

was noted for banana peel nano cellulose fibers, which is significantly low compared to micro

cellulose fibers. Oun & Rhim (2017) noted the increase of residual weight in nano cellulose

compared to their native micro samples. They attributed this increase of residual weight to

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sodium, sulphate and chloride residues in nanocellulose, presumably from the chemical isolation

process. Therefore, reduced residual weight noted in both the samples of cellulose nanofibers in

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our study, can be attributed to lack of chemical residues in cellulose molecules. This reduction of

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residual weight may also be due to loss of minerals during sonication and subsequent washing of

cellulose molecules. Initial moisture losses of 8.97 and 7.79 % (w/w) were noted for micro and

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nano cellulose fibers extracted from the banana bract. Major weight loss of 40.36 and 64.63 %

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(w/w) were noted for micro and nano cellulose fibers extracted from the banana bract. After
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major weight loss, a constant decrease in sample weight was observed till 800 ℃. The residual
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sample weight of 41.76 and 10.57 % (w/w) were noted for BB micro and nano cellulose fibers,

respectively. The thermal weight loss curves of BB cellulose nanofiber show lack of increase in
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thermal stability, but both micro and nano cellulose fibers were examined to have same
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disintegration temperature. This shows retention of thermal stability in BB nano cellulose fibers
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compared to its microform.

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Fig. 5: Thermogravimetric weight loss curves of micro and nano cellulose fibers [BP –
Banana peel; BB – Banana Bract], Black continuous line – Micro cellulose fiber; Red
dashed line – Nano cellulose fiber
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3.2.2 Differential scanning calorimetric analysis

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Differential scanning calorimetric curves of micro cellulose fibers and nano cellulose fibers were

illustrated in Fig. S6. The BP micro cellulose fibers showed an initial endothermic peak at
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around 90 ℃, corresponding to evaporation of water molecules from the sample. The major

endothermic peak with energy absorption of 681.4 J/g was noted at the peak temperature of

250.1 ℃, with onset degradation temperature around 210 ℃. Kar (2011) stated that this major

endothermic energy absorption is due to the volatility of hemicellulose like materials. The

21
degradation of cellulose molecules also corresponds to breakage of 1 - 4 glycosidic linkages

between glucose monomers and other covalent bonds within glucose monomers. Breakage of

these bonds requires a high amount of energy, consequently, the energy absorption denoted by

the major endothermic peak can be attributed to breakage of covalent bonds between and within

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glucose monomers. There was a major shift of temperature noted in endothermic and exothermic

peaks, during the degradation of banana peel nano cellulose fibers. Initial endothermic and

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exothermic peaks were observed at around 150 and 220℃, respectively. Major endothermic peak

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with energy absorption of 152.5 J/g was noted at the peak temperature of 339.5 ℃, with onset

degradation temperature around 260 ℃. Differential scanning calorimetric analysis curves of

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micro and nano cellulose fibers extracted from banana bract showed the similar pattern

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compared to banana peel cellulose molecules. The major endothermic peak was observed for
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BB-micro cellulose fibers, at the peak temperature of 285 ℃ with energy absorption of 939.4 J/g.
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This energy absorption can be attributed to the degradation of cellulose. Cellulose nanofibers

extracted from BB showed reduced energy absorption of 107.5 J/g at 342 ℃, attributed to the
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degradation of cellulose. This reduction in the endothermic peak of nano cellulose fibers can be
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attributed to lack of hemicellulose like materials (its vaporization will absorb more energy),
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which were disrupted and washed during nano cellulose preparation.

3.3 Crystallinity index of micro and nano cellulose fibers

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Fig. 6, shows the X-ray diffraction spectra of micro and nano cellulose fibers extracted from the
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banana peel and banana bract. Micro and nano cellulose fibers of banana peel showed

characteristic peaks around 12.6º (101), and 21º (002), attributing to type I cellulose

crystallographic plane (Gong et al., 2017; Nishino et al., 2004). Cellulose nanofibers were

observed to have significantly higher peak intensities compared to micro cellulose fibers. The

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intense diffraction peak noted at 21º, proves the high crystalline nature of BP nano cellulose

compared to BP micro cellulose (Gong et al., 2017; Nishino et al., 2004; Wang, Yao, Zhou, &

Zhang, 2017). Crystallinity index (CI) of 77.2 % evaluated for BP-nano cellulose fibers, was

noted to be higher than its microfibers, which was evaluated to have a CI of 61.1 %.

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Micro cellulose extracted from the banana bract showed a characteristic peak at 22.3º (002).

After particle size reduction and sonication of BB-micro cellulose fibers, the characteristic peak

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intensities were significantly improved. Crystallinity index of BB micro and nano cellulose

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fibers was estimated to be 28.6 % and 75.8 %, respectively. Therefore, the improved intensity in

characteristic peaks of BB nano cellulose fibers can be attributed to high crystalline nature of

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nanofibers. The overall increase in the crystallinity index of cellulose nanofibers can be
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attributed to the reduction of amorphous regions in cellulose (Gong et al., 2017; Leung et al.,
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2011; Zhang et al., 2017).
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Fig. 6: X-ray diffraction spectra of micro [MC] and nano [NC] cellulose fibers [BP –
Banana peel; BB – Banana Bract], Black line – Micro cellulose fiber; Red line – Nano
cellulose fiber
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3.4 Yield and degree of substitution of cellulose acetate

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The yield of cellulose acetate (CA) from BP and BB nano cellulose fibers was estimated to be

68.73 ± 1.13 and 70.25 ± 1.24 % (w/w), respectively. The yield of cellulose laurate (CL) from
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BP and BB nano cellulose fibers was estimated to be 41.59 ± 1.22 and 53.35 ± 1.20 % (w/w),

respectively.

24
NMR spectral analysis of acylated cellulose samples can be used not only for characterization,

but also to find the substitution degree for acylated cellulose (Fu et al., 2014; Kar, Liu, & Edgar,

2011; Kono et al., 2015). 13C NMR spectra of CA molecules produced from nano cellulose fibers

of BP and BB were illustrated in Fig. 7. The intense peak between 30 and 20 ppm, attributes to

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CH3 carbons present in acetyl groups attached to cellulose backbone carbons of C2, C3, and C6.

Peaks in between 60 and 100 ppm represent characteristic anhydrous glucose carbon units of

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cellulose (Fu et al., 2014; Kar et al., 2011; Singh et al., 2014). Kono et al. (2015) stated that the

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degree of substitution of any modifications in cellulose can be estimated by integration of C-O

carbon resonance peaks at 13C NMR around 180 to 170 ppm. This method works on the principle

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that both laurate and acetate of cellulose have C-O group attachments to C2, C3 and C6 carbons of

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cellulose backbone (Kono et al., 2015). Thus the integration of C-O peak directly estimates the
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amount of C-O bond present in cellulose backbone carbons. Therefore, integration of C-O
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carbon peaks was used to estimate the degree of substitution in modified cellulose molecules.

The degree of substitution of cellulose acetate produced from BP and BB nano cellulose was
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estimated to be 2.18 and 2.43, respectively. Table 1, tabulates the 1H & 13C NMR spectral
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chemical shifts δ (ppm) of cellulose acetate (CA) and laurate (CL) produced from banana peel
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and bract.
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Table 1: 1H & 13C NMR spectral chemical shifts δ (ppm) of cellulose acetate (CA) and laurate (CL) produced from banana

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peel and bract

Carbons
Sample

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C1 C2 C3 C4 C5 C6 CH2 CH3
Unit δ (ppm)
24.2 – 26.1 (m)

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Banana peel CA 100.4 (s) 74.8 (s) 73.9 (s) 88.5 (s) 72.2 (s) 63.5 (s) -
Banana Bract CA 99.7 (s) 74.2 (s) 73.8 (s) 88.7 (s) 72.5 (s) 63.6 (s) - 27.5 – 31.8 (m)
98.6 (s) 73.6 (s) 72.9 (s) 88.9 (s) 71.4 (s) 62.8 (s) 20.5 – 35.6 (m) 13.5 – 14.9 (t)

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Banana peel CL
Banana Bract CL 98.8 (s) 73.9 (s) 72.8 (s) 89.1 (s) 70.9 (s) 61.2 (s) 20.3 – 34.8 (m) 13.7 – 15.6 (t)

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Protons
H1 H2 H3 H4 H5 H6 CH2 CH3
Banana peel CA 4.47 (d) 3.75 (t) 5.09 (d) 3.29 (d) 3.51 (t) 3.6 (d) - 1.34 – 1.78 (m)
1.28 – 1.74 (m)
ED
Banana Bract CA 4.33 (s) 3.82 (s) 5.21 (s) 3.31 (s) 3.53 (s) 3.60 (s) -
Banana peel CL 3.97 (q) 3.86 (t) 4.08 (s) 3.63 (d) 3.69 (d) 3.79 (t) 1.09 – 1.18 (m) 0.68 – 0.79 (m)
Banana Bract CL 4.09 (s) 4.03 (s) 4.12 (s) 3.68 (d) 3.71 (d) 3.84 (s) 1.01 – 1.45 (m) 0.73 – 0.91 (m)
1
H NMR taken at 400.23 MHz and 13C NMR taken at 100.65 MHz.
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C3D6O was taken as solvent for CA and CDCl3 was taken as solvent for CL.
Samples were set at temperature of 296.9 K. [s – singlet; d – doublet; t – triplet; q – quartet; m – multiplet]
E
CC
A

26
1
H NMR spectra of CA molecules produced from nano cellulose fibers of BP and BB were

depicted in Fig. S7 & S8. Cellulose acetate produced from BP and BB nano cellulose fibers

showed characteristic resonance peaks of ring protons in between 2.8 and 5.2 ppm (Kono et al.,

2003; Singh et al., 2014). CH3 proton resonance peaks were found to be between 0.8 and 1.5

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ppm, corresponding to the acetyl groups associated with cellulose acetate (Kono et al., 2015).

The additional solvent peak of acetone associated protons was also noted. Resonance peaks of

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ring protons showed the complex pattern with the presence of doublet and triplet resonance for

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each proton. These complex patterns in resonance of ring protons are in agreement with the

findings of Kono et al. (2015).

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Fig. 7: 13C NMR spectra of cellulose acetate [CA] produced from cellulose nano fibers [BP
– Banana peel; BB – Banana Bract]

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Fig. 8, shows 13C NMR spectra of cellulose laurate produced from BP and BB nano cellulose

fibers. The corresponding CH3 and CH2 carbon resonance peaks were found to be between 10

and 35 ppm. These resonance peaks were attributed to laurate molecules, bonded with cellulose

backbone carbons of C2, C3, and C6 (Singh et al., 2014). Resonance carbon peaks of cellulose

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rings were found between 60 and 100 ppm. Carbon resonance peaks associated with C-O bonds

were found between 180 and 170 ppm. These C-O resonance peaks can be attributed to laurate

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attachment with cellulose backbone (Kar et al., 2011; Kono et al., 2015; Singh et al., 2014). The

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degree of substitution for cellulose laurate produced from BP and BB nano cellulose fibers was

estimated to be 2.12 and 2.34, respectively. Fig. S9 & S10 illustrate the 1H NMR spectra of

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cellulose laurate produced from BP and BB nano cellulose fibers. The characteristic proton

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resonances of anhydrous glucose units in cellulose laurate were found to be between 3 and 4.2
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ppm. CH3 and CH2 proton resonances of laurate unit were noted to be between 0.6 - 1 ppm and 1
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– 1.4 ppm, respectively. Other protons associated with laurate-cellulose bonding were found

between 1.4 and 2.4 ppm (Singh et al., 2014). Thus, acetyl and lauroyl conversion of cellulose
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molecules were confirmed through NMR spectra of 13C carbon and 1H proton resonances.
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Fig. 8: 13C NMR spectra of cellulose laurate [CL] produced from cellulose nano fibers [BP
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– Banana peel; BB – Banana Bract]

3.5 Thermal analysis of Cellulose acetate
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Fig. 9, shows the thermal analysis curves of cellulose acetate (CA) produced from BP and BB
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nano cellulose fibers. The thermal weight loss curve of BP-CA showed initial moisture loss of ~5

% (w/w) at 95.31 ℃. Major weight loss of 61.98 % (w/w) corresponding to degradation of CA,
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was noted between 235 and 343 ℃, with peak disintegration temperature of 308 ℃. The thermal
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weight loss curve of BB-CA showed a major weight loss of 41.45 % (w/w) between 144 and 242

℃, with peak disintegration temperature of 206 ℃. DSC curves (Fig. S11) of both BP-CA and
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BB-CA showed two distinctive endothermic peaks. Among them, initial can be attributed to

cleavage of the acetyl group from the cellulose backbone. The second endothermic peak can be

attributed to the degradation of cellulose. The onset degradation temperature of BP-CA and BB-

CA was estimated to be ~245 and 180 ℃, respectively.

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Fig. 9: TGA & DTG thermal analysis curves of cellulose acetate [CA] produced from nano
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cellulose fibers [BP – Banana peel; BB – Banana Bract], Black continuous line – TGA; Red
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dashed line – DTG

Fig. 10, shows the thermal analysis curves of cellulose laurate (CL) produced from BP and BB
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nano cellulose fibers. The thermal weight loss curve of BP-CL and BB-CL showed a major
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weight loss of 61.47 and 82.14 % (w/w), respectively. The peak disintegration temperature for

BP-CL and BB-CL was examined to be 264 ℃ and 370 ℃, respectively. Differential scanning
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calorimetric curve (Fig. S12) of cellulose laurate samples showed two distinct endothermic

peaks, corresponding to cleavage of lauroyl group and disintegration of cellulose (Spinella et al.,

2016). Onset disintegration temperature of BP-CL and BB-CL was found to be ~180 and 150 ℃,

respectively.

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Fig. 10: TGA & DTG thermal analysis curves of cellulose laurate [CL] produced from
nano cellulose fibers [BP – Banana peel; BB – Banana Bract], Black continuous line –
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TGA; Red dashed line – DTG

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4 Conclusions
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We have developed a method for extraction of micro and nano cellulose fibers from agro-based

industrial wastes. Microwave digestion method was found to be effective for the production of
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micro cellulose fibers. Ball milling assisted sonication treatment of micro cellulose fiber was

proved to be a potential method for production of nano cellulose fibers. Banana peel and bract
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were estimated to have a high amount of cellulose content. Cellulose nanofibers extracted from

banana peel and bract was examined to be a potential source for production of acetyl and lauroyl

cellulose. The modified cellulose nanofibers, with high thermal stability, can serve as a potential

31
replacement for synthetic petrochemical polymers. Being a biodegradable polymer, modified

cellulose can reduce the accumulation of petrochemical plastics in the environment.

5 Acknowledgments

We would like to acknowledge funding from the University grand commission (UGC), New

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Delhi (UGC/MRP/MAJOR/BIOT/2013/19727).

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