Carbohydrate Polymers

Optimization of the Alkali Treatment on the Tempo-Modified Cellulosic Nanofillers in

Autoclaved Epoxy Matrix
--Manuscript Draft--

Manuscript Number:

Article Type: Research Paper

Keywords: Moringa Oleifera; Activation energy; Reinforcement; Epoxy; Water resistance;

Composites

Corresponding Author: Kajal Mishra

Indian Institute of Technology Roorkee
Roorkee, - INDIA

First Author: Kajal Mishra

Order of Authors: Kajal Mishra

Shishir Sinha

Abstract: Investigators increased interest in composites with novel natural fibres beholds
significant progress globally over the past decade. Moringa oleifera seed filler (MOSF)
is among the few newly known novel fibre-rich in cellulose and meagrely used in
commercial industries. This research article used a broad characterization of 2,2,6,6-
TetraMethyl-1-PiperidinylOxy (TEMPO)-modified Moringa Oleifera cellulosic nanofiller
(TMCF)/epoxy composites to verify its potential as a feasible substitute for synthetic
fibres in polymer composites. Composites were fabricated at a fixed filler size of 300-
500 µm with a loading of 15 wt. % untreated and alkali-treated composites through the
two processes: hand lay-up followed by autoclave curing. Composites with 5 wt. %
alkali treatment TMCF loading possesses superior water resistance, interfacial surface
chemistry, and mechanical property compared to autoclaved epoxy and the untreated
composite. Four isoconversional methods, Friedman, Coats-Redfern, Broido, and
Kissinger, were utilized to investigate the degradation behaviour and kinetic
parameters like activation energy of composites.

Suggested Reviewers: Dr. Ashutosh Tiwari

tiwari@eng.utah.edu

Dr. Simant Upreti

supreti@ryerson.ca

Dr. Kumar Patchigolla

k.patchigolla@cranfield.ac.uk

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Cover Letter

To

The Editor

Carbohydrate Polymers

Dear Sir/Ma’am

Please find enclosed herewith our manuscript entitled “Optimization of the Alkali Treatment on
the Tempo-Modified Cellulosic Nanofillers in Autoclaved Epoxy Matrix“ for the possible
publication in Carbohydrate Polymers. This paper has been co-authored by Prof. Shishir Sinha,
Department of Chemical Engineering, Indian Institute of Technology Roorkee, India. The gaps of
the research from the previous literature are as under.
 Abundantly available, novel and inexpensive Moringa Oleifera seed filler has been
characterized for possible reinforcement polymer composite.
 Many works has been reported on the mechanical and structural properties of the
composites but less literature is available on the influence of surface modification of these
composites.
 This paper focuses on the thermal degradation, barrier and interfacial capabilities of the
fabricated composites to get usage in the real world problems.

We declare that this manuscript, has not been published before and is not currently being
considered for publication elsewhere.

We know of no conflicts of interest associated with this journal and there has been no financial
support for this work that could have influenced its outcome. As corresponding author, I confirm
that the manuscript has been read and approved for submission by all the named authors.

Thanking You
With regards
Ms Kajal Mishra
Research Scholar
Department of Chemical Engineering
Indian Institute of Technology, Roorkee (India).
Email: kajjalmishra@gmail.com
Manuscript Click here to view linked References

1 Optimization of the Alkali Treatment on the Tempo-Modified Cellulosic Nanofillers in

2 Autoclaved Epoxy Matrix

3 Kajal Mishra1, Shishir Sinha1*

1*
4 Department of Chemical Engineering, Indian Institute of Technology Roorkee,

5 Roorkee-247667, India

6 shishir@iitr.ac.in

7 Corresponding author: * kajjalmishra@gmail.com

10 Abstract

11 Investigators increased interest in composites with novel natural fibres beholds significant progress

12 globally over the past decade. Moringa oleifera seed filler (MOSF) is among the few newly known

13 novel fibre-rich in cellulose and meagrely used in commercial industries. This research article used a

14 broad characterization of 2,2,6,6-TetraMethyl-1-PiperidinylOxy (TEMPO)-modified Moringa

15 Oleifera cellulosic nanofiller (TMCF)/epoxy composites to verify its potential as a feasible substitute

16 for synthetic fibres in polymer composites. Composites were fabricated at a fixed filler size of 300-

17 500 µm with a loading of 15 wt. % untreated and alkali-treated composites through the two

18 processes: hand lay-up followed by autoclave curing. The interfacial surface compatibility of the

19 cellulosic nano-fillers/epoxy composite was analyzed through X-ray photoelectron spectroscopy. The

20 other properties, such as water uptake rate, static and dynamic mechanical properties and thermal

21 stability, have been studied for untreated and treated composites. Composites with 5 wt. % alkali

22 treatment TMCF loading possesses superior water resistance, interfacial surface chemistry, and

23 mechanical property compared to autoclaved epoxy and the untreated composite. Four

24 isoconversional methods, Friedman, Coats-Redfern, Broido, and Kissinger, were utilized to

25 investigate the degradation behaviour and kinetic parameters like activation energy of composites.

1
26 Composites that have been 5 wt. % mercerized exhibit greater thermal resilience and activation

27 energy of 250 kJ/mol, which is 20% greater than the untreated sample. This study validates the 5 wt.

28 % alkali treated TMCF as a novel sustainable and bio-reinforcement in polymer composite for semi-

29 structural applications.

30 Keywords: Moringa Oleifera; Activation energy; Reinforcement; Epoxy; Water resistance;

31 Composites

32 Introduction

33 For sustainable development, academicians and researchers are looking for materials that are

34 renewable, cost-effective, nature friendly, and energy-saving. Natural fibers have the edge over

35 synthetic fibers (glass, carbon, aramid, etc.), which are acquired from petroleum sources whose

36 usability is diminishing day-by-day. Being economical, lightweight, low density, easily accessible,

37 renewable, and biodegradable natural fibers overlap the synthetic fibers. It is also being used as an

38 alternate in different industries such as automobile and other manufacturing industries [Koronis et al.

39 2013] . Several reviews are accessible on the reinforcement of natural fiber in various polymer

40 matrix with their properties. Studies and application of established natural fiber such as Rice husk,

41 cotton, jute, coir, kapok, ramie, flax, etc. have already been reported in the literature [Faruk et al.

42 2012; Mittal et al. 2016; Saba et al. 2016] . The utmost issue associated with using natural fiber-

43 based polymer matrix is the poor affinity between filler/fiber and matrix. To outclass this problem,

44 different surface treatment strategies are available. Investigators are now looking into using locally

45 accessible unique natural fiber that has a variety of uses and remarkable characteristics to support

46 and improve rural economies and a variety of applications.

47 Acacia leucophloea fibres were extracted by the degumming process and described that the fibre

48 crystallinity index was 51%. Afterwards, it was favourably used as a reinforcement in the epoxy

49 matrix [Arthanarieswaran et al. 2016; Arthanarieswaran et al. 2015]. Cellulose fibres were extracted

2
50 from the Saharan aloe Vera cactus plant by the water retting process. It was eventually revealed that

51 the fibre's degree of crystallinity and crystallite size, 52.8 % and 5.6 nm, respectively, were suitable

52 for strengthening material in the composite material [Balaji and Nagarajan 2017]. A novel cellulosic

53 biomass fibre made from Juncus effuses was tested for thermal properties and considered suitable for

54 strengthening material in polymer composites [Maache et al. 2017]. Phoenix Sp. Fibre's

55 physicochemical components were examined in investigations, and it was discovered that the fibre

56 has a crystallinity value of 57 %. Additionally, it was mentioned that it could work more as an

57 affordable, eco-friendly bio-composite [Rajeshkumar et al. 2017]. The effect of fibre loading with

58 different particle sizes was studied on new fibre, i.e., Areca palm leaf stalk [Shanmugasundaram et

59 al. 2018]. The extraction of cellulosic fibre from Coccinia grandis.L. by biological retting process

60 was carried out, and very high cellulose content (62.35 wt %) was observed, which confirmed its

61 suitability as a material for reinforcement in the polymer matrix [Senthamaraikannan and Kathiresan

62 2018]. Delonix regia seed fillers were reinforced with recycled low-density polyethylene (LDPE)

63 through a compression moulding process. In comparison to the neat LDPE matrix, it was discovered

64 that the composites had increased tensile and flexural characteristics [Agunsoye et al. 2019]. The

65 polypropylene matrix material was used to strengthen the mimusops elengi seed fibre. Morphological

66 characteristics revealed that the fibres adhere well to the matrix material, increasing the material

67 characteristics such as mechanical and structural properties [Muniyadi et al. 2018]. The discussion

68 above makes clear that scientists are actively researching innovative fibres that are readily accessible.

69 On the other hand, few papers are accessible on these fibers' activation energy and thermal kinetics.

70 A thermal kinetic model studied the activation energy of PLA (polylactic acid) composite reinforced

71 with hemp fibres. Flynn-wall-Ozawa (FWO) method was used to calculate the activation energy of

72 the composites [Oza et al. 2014]. Few researchers carried out an analysis of the thermal aspect of

73 sisal fibre with polyester composite. Mercerization was carried out to see its effect of it on the

74 activation energy. It proved that treated fibre enhances the activation energy, ultimately increasing

3
75 thermal stability and moisture absorption [Sreekumar et al. 2008]. The activation energy of alkali and

76 acid-treated bagasse lignocellulosic fibre was compared through thermal degradation kinetics and

77 concluded that alkali-treated bagasse fibre has more considerable activation energy compared to

78 acid-treated [Motaung and Anandjiwala 2015].

79 Despite cellulose having demonstrated exceptional qualities, the extraction process is frequently

80 hampered by several inherent characteristics of cell walls. Covalent bonds between cellulose,

81 hemicellulose, and lignin as well as the packed cell wall topology that limits cellulose availability,

82 are among the technological challenges to be addressed [Senthamaraikannan and Kathiresan 2018].

83 Pre-treatment is now necessary for producing cellulose, making succeeding procedures (like

84 chemical reagent removal) more effective [Muniyadi et al. 2018]. When used as a pre-processing, the

85 ultrasonication process of raw fillers demonstrated its viability. It encouraged the discharge of

86 hemicelluloses and lignin while improving the availability and reaction of the cellulose [Sreekumar

87 et al. 2008]. Apparently, there is only minimal study on how ultrasonication in the extraction process

88 affects the obtained cellulose. Therefore, this study looked into the effects of

89 ultrasonication technology on the characteristics of the cellulose that are produced. However, the

90 cellulose in its raw form is not prepared for efficient responses, and some adjustments may be

91 needed to stimulate the cellulosic ability. To create cellulose variants by altering their interface

92 through the 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-modification is a viable

93 technique. The opposite charges of carboxyl groups that the TEMPO-modified cellulose

94 fillers (TMCF) create uniform TMCF suspensions that are stabilised by surface charge. There are

95 few findings on the temperature stability, activation energy and dynamic mechanical characteristics

96 of TMCF-based composites. As a result, a thorough knowledge of the dynamics of TMCF

97 composites is needed when temperature-dependent features, mechanical, and structural properties are

98 combined.

4
 99 The literature survey supports the scrutiny of novel and economical natural fibres, which are being

100 used productively in polymer composite. These serve the environmental benefits, furnish

101 multipurpose uses, and primarily evolve the economy of developed and developing countries of the

102 rural region. This research focuses on the extensive characterization of novel filler moringa oleifera

103 seeds of a "multi-function" tree known as Moringa Oleifera Lamarack (MOL), or Moringa

104 ptreygosperma Gaertner belongs to moringaceae ancestry. They are commonly called a horse-radish

105 tree (resembles the taste of sauces and spices prepared from the roots), drumstick tree (resembles

106 pods shape). They also have country-specific names such as Sahajana (India), Kelor (Indonesia),

107 Saijana (Pakistan), Zogale (Northern Nigeria), and many others, which indicates the excellence of

108 the tree all over the world [Fuglie 1999]. MOL is a meridional shrub that originates from the

109 Himalayan trail of the sub-tropical and tropical regions of Pakistan, Afghanistan, Arabia,

110 Bangladesh, Africa, North America, and the South Philippines [Mughal et al. 1999]. Lately, MOL

111 has acknowledged more massive acceptance worldwide due to its resistance to variable temperature

112 conditions, reasonably dry soils, and active and straightforward flourishment in the area's

113 unpredictable circumstances, state, and topographical space [Gopalakrishnan et al. 2016]. The seeds

114 of Moringa Oleifera have engaged scientific attention due to its macro-nutrient configuration, oil

115 extraction capability, and significant production of protein. Considerable investigations have

116 reported that phytochemical compounds and hydroxy metabolites present in seeds have meaningful

117 antioxidant actions and have been used as bioceutical alternatives. Moringa oleifera seeds consist of

118 4.48-4.89g/100g of overall phenolic compounds, out of which gallic, ellagic, and caffeic acid

119 dominate. The other phenolic compounds are present in smaller amounts, such as ferulic, p-

120 coumaric, cinnamic acids, and several others [Saa et al. 2019]. Also, seeds consist of "Behen oil,"

121 used in many pharmacological activities like antimicrobial and antifungal agents [Ramachandran et

122 al. 1980]. Moreover, oil was also used as a substitute for producing biodiesel and treating arthritis,

123 high blood pressure, and rheumatic disorders [Mahmood et al. 2010]. Several applications

5
124 of Moringa Oleifera seeds in the field of water treatment and water purification are available.

125 Researchers have exposed its adequacy in treating impurities, low, medium, high turbidity, pH,

126 alkalinity, acidity, and hardness of water [Tunggolou and Payus 2017; Babu and Chaudhuri 2005;

127 Amagloh and Benang 2009; Daniyan et al. 2011; Mangale et al. 2012]. Additionally, the seed

128 powder acts as a natural coagulant, removing heavy metals from the water, and serves as a

129 dewatering agent [Hendrawati et al. 2016; Okuda et al. 1999].

130 In summary, it can be said that while Moringa Oleifera seed extract has been studied in various

131 sectors, no research has been done on its unique properties as a filler strengthening material in

132 composites. Also, we anticipate that the ultrasonication pre-treatment will influence TMCF's

133 crystallinity and thermal stability and that the alkali treatment concentration will impact the TMCF

134 composites' mechanical characteristics. This study intends to optimise and investigate the effects of

135 alkali treatment and ultrasonic extraction conditions with TEMPO-modification on the cellulose

136 chains of Moringa Oleifera and the structural and barrier characteristics of the resulting TMCF

137 composites. As a result, by illuminating the relationship between the structural, mechanical and

138 thermal characteristics of TMCF composites, this work can contribute to the body of knowledge on

139 cellulose usage.

140 Material and methods

141 Material Used

142 Moringa oleifera seeds were purchased from Shiv Shyam Sales Corporation, Chandni Chowk, New

143 Delhi, India. Firstly, seeds were washed stringently with distilled water to remove the surface

144 impurities, then sun-dried for 24 h to remove residual moisture. Seeds were then kept in the soxhlet

145 apparatus to extract the oil. Later, the remaining oil-free seeds from the instrument were kept in an

146 electric oven at 60ºC for 72 h to dry. The dried seeds were subsequently cut into small pieces and

147 powdered in an electric grinder and then through high energy ball mill obtained a substantial fraction

6
148 of 300-500 nm. Finally, fillers were air-dried at 110 ºC for 2 h and stored in the dry atmosphere until

149 further processing. The matrix epoxy consists of epoxy monomer diglycidylether of bisphenol-A

150 (AW106) (EEW of 214-221 g/eq) [Huntsman 2011] and polyaminoamide hardener (HV 953)

151 acquired from Huntsman International Private Limited, Mumbai, India. The stoichiometric ratio of

152 mixing, as suggested by the supplier, is 5:4 v/v [Huntsman 2011]. All other analytical-grade

153 chemicals are procured from HiMedia Laboratories Pvt. Ltd.

154 Extraction of cellulose nano-fillers from Moringa oleifera seed through various surface

155 modification

156 With slight alterations, the cellulose extraction followed the literature [Hu et al. 2010; Martínez-Sanz

157 et al. 2015]. The process for extracting cellulose from Moringa Oleifera mainly involved the

158 following steps: i) preparation using ultrasound; ii) treatment with sodium chlorite; and iii)

159 mercerization with different concentrations.

160 i) Pretreatment with ultrasonication: The nano-size crushed Moringa Oleifera powder was mixed to

161 deionized water in the ratio of 2:10 (g/mL). A high-energy ultrasonic cell disruptor (JY92-IIN,

162 China) with a 15 mm titanium blade was then used to disrupt the combination. The ultrasonic

163 battery's energy was fixed to 630 W, and it ran for 10 minutes while treating for 4 sec and cooling for

164 2 sec at a time. In a water bath, the modified mixture was heated to 90 °C for 3 h. The

165 material was then filtered, recovered, and cleaned with ethanol and distilled water.

166 ii) Treatment with sodium chlorite: After the ultrasonication procedure, the specimens were dried in

167 a hot air oven at 70 °C until their weight was stable and then blended with a 7.5% sodium chlorite

168 (NaClO2) solution in the ratio of 2:10 (g/ml) at a pH of 3.5–4.2 for 3 h. Distilled water was used to

169 sieve and clean the blend until the pH reached neutral. The insoluble residual material was then dried

170 at 70 °C till it reached a consistent weight.

7
171 ii) Treatment with alkali solution: the residual material that was obtained in step ii) was immersed in

172 5wt. % and 10wt. % sodium hydroxide solutions for 1.5 h while maintaining a 20:1 alkaline solution

173 to filler ratio. Afterwards, it was rinsed with acetone and deionized water 4-5 times until a constant

174 pH was achieved before being dried for 55 hours at a continuous temperature of 80°C in a drying

175 oven.

176 TEMPO-modified cellulosic nanofillers (TMCF)

177 Typically, 2.0 g of nano- cellulose was mixed in 150 mL of distilled water containing 0.0175 g of

178 TEMPO and 0.2 g of NaBr before being magnetically stirred to create a homogeneous blend.

179 Subsequently, 2.5 mL of NaClO solution was mixed with the blend. At 400 rpm, the

180 modification process was conducted in a magnetic stirrer. By adding an alkaline solution

181 (0.05 mol/L), the pH of the solution was kept within the range of 8-10. Typically, 2.0 g of nano-

182 cellulose was mixed in 150 mL of distilled water containing 0.0175 g of TEMPO and 0.2 g of

183 NaBr before being magnetically stirred to create a homogeneous blend. Subsequently, 2.5 mL

184 of NaClO solution was mixed with the blend. At 400 rpm, the modification process was conducted in

185 a magnetic stirrer. By adding an alkaline solution (0.05 mol/L), the pH of the solution was kept

186 within the range of 8-10. Pure ethanol (20 mL) quenched the process while the pH held steady.

187 Filtration was used to segregate the mixture, and the residues were periodically washed to get the pH

188 down to 6.5. The specimen was then dried and froze.

189 Fabrication of the Composites

190 The epoxy resin (AW 106) and hardener (HV 953) were combined in the proportion of 5:4 (as

191 recommended by the manufacturer) to build the composite material, which was then stirred at 2200

192 rpm for 15–20 minutes. The complete mixture was sonicated and then laid on the 300×300×10 mm3

193 dimension mould and kept for curing at room temperature for 24 h. A simple hand layup setup was

194 used to develop the matrix; Teflon ® sheets were placed in a neat and stale mould to prevent the

8
195 mixer from sticking to the mould edges, followed by pressing the sheets with heavy rollers to avoid

196 the bubbles and void spaces. With a dwell duration of 200 mins, each at 80 °C, lay-up is autoclaved

197 and cured at a pressure of around 0.8 MPa. Lastly, a net load of 30 kg was placed on the mould for

198 48 h; afterwards, the developed composite sheets were removed from the mould for cutting

199 objectives as per ASTM standards for characterization purposes. Figure 1 shows the fabrication

200 process.

201

202 Figure 1: Process diagram illustrating the nanocellulose filler-based epoxy composites.

203 Methods Used

204 Compositional analysis of Moringa Oleifera seed filler (MOSF) [ Bledzki et al. 2010]

205 The Bledzki method [Bledzki et al. 2010] was used to measure the percentages of cellulose,

206 hemicellulose, lignin and ash. Eq. (1) was then used to compute the yield of extracted cellulose.

9
 Q1
207 Yield (%)  X 100 (1)
Q2

208 Where Q1 (g) represents the initial grade of Moringa Oleifera and Qg (g) represents its ultimate

209 quantity following alkali treatment.

210 Physical characteristics of the Moringa Oleifera seed filler

211 The density of nano-cellulose was estimated in the present investigation study by obtaining a

212 measurement from the 10 repetitions, and the mean findings were presented. Because the filler size

213 and form made assessment challenging, both the bulk and true density were determined. After being

214 immersed in acetone, the fillers were formed in a circular shaft underneath a load of 5 MPa. The bulk

215 density was then computed utilizing weight to volume concentration, and the Archimedes

216 method was used to estimate the true density with air and water as the operational medium. [Devnani

217 and Sinha 2019]

218 Using the given formula, the porosity was determined from the estimates of the theoretical and actual

219 densities [Joshi et al. 1993]

T
220  1 X 100 (2)
A

221 Where ε, ρT and ρA are the porosity, bulk/theoretical density (kg/m3) and actual/apparent/true

222 density (kg/m3), respectively.

223 The angle of repose was estimated through a cylindrical-shaped casting plate with a 60mm radius (R)

224 and 160 mm height (H). The cylindrical tube was set on a tabletop, loaded with caper, and

225 progressively elevated until a cone-shaped arrangement of material was developed. The degree of

226 repose was computed using a formula developed by Amin et al. (2004) [Amin et al. 2004].

 4H 
227 Degree/angle of repose (θ) = tan 1   (3)
 R 

10
228 Carboxylate content, zeta potential, degree of oxidation and polymerization

229 An old approach used conductimetric titration to analyze the carboxylate concentration and degree of

230 oxidation of the TEMPO-modified nano-cellulose [Curvello et al. 2022]. 50 ml of distilled water

231 were used to dispense in 0.2 g of dried and frozen TMCF. The pH was then brought down to 3.5

232 using 0.4 mol/L of HCl solution and 300 L of 0.2% NaCl solution. The titration was then carried out

233 at a rate of 0.5 mL/min using a mixture of 0.2 mol/L NaOH. Using Eq. (4), the carboxylate

234 concentration was determined.

C  (T2  T1 )
235 Carboxylate content (mmol COO-/g filler) =  1000 (4)
WD

236 Using Eq. (5), the degree of oxidation (DO) was determined.

162  C  (T2  T1 )
237 Degree of oxidation = (5)
WD  36  C  (T2  T1 )

238 After being immersed in 60 mL of 1 M cupriethylene diamine for 40 min, dried-freeze TEMPO-

239 modified nano-cellulose (0.5 g) were measured for their internal viscosities using a Cannon Fenske

240 capillary viscometer. Eq. (5) [Sihtola 1963] was used to determine the degree of polymerization (DP)

241 estimate, where ƞ is the mean intrinsic viscosity determined from triplicate measurements.

242 DP 0.905  0.75  [ ] (6)

243 Using the Zeta Nano Analyzer (ZS-90, Malvern Instruments, UK), the zeta potential (ζ) of 0.02%

244 (w/v) of TMCF was determined. The result represented the mean of the triplicates.

245 Static and dynamic mechanical characteristics

246 The static mechanical property tester (2716-002 Instron Model 5982, Grove City, PA, USA) was

247 used at a crosshead speed of 1 mm min-1, 2 mm min-1, and a gauge length of 50mm for the flexural,

248 tensile testing of the MOSFC using the standard as per ASTM D790 and ASTM D3039,

11
249 respectively. The specimen’s size for the mechanical testing was 250mm x 25mm x thickness for

250 tensile analysis and 100mm x 25mm x thickness for flexural analysis. The samples were produced in

251 quadruplets, and the outcome was calculated using the mean amount. According to ASTM D5023,

252 the most substantial composite with pure epoxy has been investigated by DMS Instrument (Creator:

253 Hitachi). The specimen size was 65 mm x 13 mm x 3 mm, and the tests were carried out in the

254 triaxial compression phase in the temperature range of 20-200°C at a heating rate of 4°C/min and

255 frequency of 2 Hz

256 Scanning electron microscopy (SEM)

257 The microstructural investigation was determined by SEM (LEO 435 VP), with acceleration voltage

258 till 30kV and magnification of 10x – 300 kx. A fine gold layer was covered through a sputter coater

259 over the sample to improve the conductivity before the images were taken.

260 Atomic Force Microscopy (AFM)

261 For treated and untreated MOSFC, NT-MDT (creator: NTEGRA, Series: Prima) was used to

262 measure the surface roughness and conduct atomic force microscopy (AFM) to determine the surface

263 structure. It comprises a striking phase using a silicon beam with a scanning speed and size of 0.65

264 Hz and 30 X 30 μm.

265 Fourier transform infrared spectroscopy (FTIR)

266 Nicolet of the 6700 model was used to evaluate the FTIR spectrum of the treated and untreated

267 MOSF. Small pellets were created by compressing the thoroughly ground filler at a ratio of 1:9 with

268 a reference material (KBr). The spectra of these pellets were then investigated with a resolution of 4

269 cm-1, ranging from 300 cm-1 to 4000 cm-1.

270 X-ray diffraction (XRD)

271 The crystalline phase and structure of the crystals were examined using X-Ray Diffraction (XRD).

272 The treated and untreated MOSF, XRD investigation was carried out using a German-made Rigaku

273 Ultima IVX-ray diffractometer using copper to potassium irradiation ( λ= 1.55 Å ) at 50 kV and 40

12
274 mA. The specimens were tested at a 2θ range of a goniometer rate of 3°/min between temperatures of

275 0 to 60° C. The mathematical methodology was used to calculate the crystallinity index (C.I.) [Yao

276 et al. 2008]:

I Cryst  I Amor
277 C.I .  (7)
I Cryst

278 Where IAmor was the lowest peak at 2θ among 15° and 20° and ICryst was the most significant peak for

279 extremely crystalline cellulose-(I) at 2θ among 21° and 24°.

280

281 X-ray photoelectron spectroscopy (XPS) analysis

282 The XPS analysis was used to examine the surface chemistry of the treated and untreated MOSF.

283 The information was obtained on a Kratos Axis ULTRA X-ray Photoelectron Spectrometer

284 integrated with a 175 mm electron energy analyzing device and uses monochromatic radiation Al-K

285 X-rays (1486.6 eV) at 160 W (20 kV, 20 mA). Comprehensive scans were taken at 160 eV and

286 narrow scans at 10 eV. Before the analysis, the specimen's surface was purified with Ar gas to

287 remove the impurities.

288 Thermogravimetric analysis (TGA) and activation energy

289 The nitrogen gas flow rate was maintained at 300 ml/min while the thermogravimetric study was

290 done out in an EXSTAR (Series: 6300 RT). The specimens (5-12 mg) were heated at 5, 10, and 20

291 °C/min heating rates between ambient temperature to 900 °C. In addition to mechanical qualities, it

292 is crucial to study composite materials' thermal degradation and activation energy to improve their

293 suitability for use when being subjected to higher temperatures is necessary. The activation energy of

294 the decomposition rate measures the thermal decomposition characteristic and composites' resilience.

295 Therefore, the two integral approaches C-R (Coats-Redfern) and Kissinger technique, as well as two

296 differential techniques Freidman and Broido procedure, were used to analyze the deterioration

297 pathway and activation energy of the composites [Indran and Edwin 2015].

13
298 The kinetic equations for Kissinger (8) and Coats-Redfern (C-R) (9&10) techniques are as follows,

299 respectively.

300

   E  AR 
301 ln  2   k  ln   ; [(ln(β/Tm2) versus 1/T] (8)
 Tm  RTm  Ek 

1  (1   ) (1n )   AR  2 RT  Ek
302 ln    ln  1    ; (for n≠1) (9)
 (1  n)T  Ek
2
  Ek  RT

  ln( 1   )   AR  2 RT  Ek
303 ln    ln  1    ; (for n=1) (10)
 T   Ek
2
 Ek  RT

304 The heating rate (K/min), activation energy (KJ/mol), order of reaction, and temperature at the

305 highest rate of weight loss are represented by β, Ek, n, and Tm, respectively.

306 The differential kinetic equations for Freidman (11) and Broido (12) techniques are as follows,

307 respectively

 dx  E
308 ln    ln[ Af ( x)]  k ; [ln(dx/dt) versus 1/T] (11)
 dt  RT

  1  E  RZTm2 
309 ln ln     k  ln   ; [ln[ln(1/Y) versus 1/T] (12)
  Y  RT  k 
E 

310 The degree of conversion, the fraction of original molecules that haven't yet deteriorated, the heating

311 rate (ᴼC/min), and the frequency value are represented by the variables x, Y, and Z. (S-1)

312 Water absorption rate of Moringa Oleifera seed filler composite (MOSFC)

313 The ASTM D570 standard was used to execute the water absorption measurement. The

314 squared specimens’ dimensions were 20mm x 20mm. The heating compartment was set at 60°C

315 while the composites were filled with varied filler quantities (5 wt. % to 25 wt. %). Followed by

316 subsequent specimen measuring, the specimens were subjected to two different media containing

317 distilled water (pH=6.5) and saline water (pH=8). After thoroughly washing them with absorbent

14
318 paper, the weight intake was consistently noted. Until a persistent weight was reached, specimens

319 were taken in quadruplets, and the procedure was followed.

320 The % water gained was calculated through [Shakeri and Ghasemian 2010]:

𝑋1−𝑋0
321 𝑤𝑎𝑡𝑒𝑟 𝑔𝑎𝑖𝑛 (%) = 𝑥 100 % (13)
𝑋0

322 Where X1 and X0 are final weight at time t and dry weight initially, respectively.

323 The thickness swelling % was calculated through [Shakeri and Ghasemian 2010]:

𝑍1−𝑍0
324 𝑇ℎ𝑖𝑐𝑘𝑛𝑒𝑠𝑠 𝑠𝑤𝑒𝑙𝑙𝑖𝑛𝑔 (%) = 𝑥 100 % (14)
𝑍0

325 Where Z1 and Z0 are thickness post and pre to soaking.

326 Contact angle analysis of Moringa Oleifera seed filler composites

327 Under limited environments, water's static and dynamic contact angles were evaluated on Moringa

328 Oleifera seed filler-based epoxy composites using a tensiometer (Model: Krüss, Series: K100) and

329 the Wilhelmy method. As per Van Oss's concept [Oss 1993] employing the program SurfTen 4.3 and

330 the scale suggested by Della Volpe et al., 2015 [Della and Siboni 2015], the preference of liquid is

331 determined by the variation in surface energy aspects among composites.

332 Results and Discussion

333 Physical and Compositional analysis of Moringa Oleifera seed fillers

334 It's crucial to validate the contents of cellulosic and hemicellulosic concentrations with lignin and ash

335 to comprehend the chemical analysis of the raw and modified filler. Table 1 displays the relative

336 findings of the current investigation. In the present research, the untreated filler has a concentration

337 of 5.09±0.87 ash, 10.45±0.71 lignin, 15.37±0.98 hemicellulose, and 34.71±0.94 cellulose. The

338 cellulose and hemicellulose constituents are analogous to Mishra and Sinha's findings [Mishra and

339 Sinha 2020]. The cellulose and ash compositions are consistent with results from the previous study

15
340 by Sharma et al., 2020 although the hemicellulose constituent is significantly lower than that of other

341 researchers' reports [Sharma et al. 2021]. According to Kalaf et al., 2018, [Khalaf et al. 2018], the

342 percentage of cellulose and hemicellulose were 4.63% and 5.69%. In contrast, lignin and ash were

343 2.57%, and 3.78%, respectively, which are substantially lower than those investigated in the present

344 research. Results are comparable with previous research, and the variability in holocellulosic

345 concentration may result from inter-species changes. To improve the filler to polymer adhesion, the

346 filler underwent chemical alteration. As an outcome, the filler and polymeric structures effectively

347 assign stress loads, boosting composites with greater structural rigidity [Sarikanat et al. 2014; Dalmis

348 et al. 2020]. Table 1 demonstrates that the seed filler acquired a significant concentration following

349 the chemical interaction as a pollutant, lignin, oily, and hemicellulose contents are eliminated. This

350 contains details on the general increase in cellulose constituent in fillers. This implies that the filler's

351 crystallite component increases with increasing cellulose, which eventually aids in forming superior

352 composites [Fajobi et al. 2022]. Treatment smoothens the filler layer by eliminating pollutants,

353 greasy substances, lignin, and hemicelluloses. All doses of alkali modification eliminated the non-

354 lignocellulosic component of filler, although 5% w/v alkali concentration eliminated most of this.

355 The greater concentration (10% w/v) of alkali may cause a reduction in the cellulosic matter [Rokbi

356 et a. 2011]. With different alkali treatments, the cellulose yield varied from 33.50% for no

357 treatment to 36.53% for 5 wt. % treatment. The cellulose yield increased significantly for 5% of the

358 alkali treatment and dropped by 10 wt. %. This result showed that the alkali treatment improved the

359 cellulosic yield and achieved the suppleness of the raw filler. The cavitation impact of

360 ultrasonication, which can encourage the elimination of lignin and hemicellulose, boosted the mass

361 transfer of sodium chlorite and alkaline solution (after ultrasonic pre-processing).

362 The bulk density of Moringa Oleifera filler is 0.79 ± 0.34 g/cm3 (Table 2). Bulk density

363 specification is crucial since it establishes the depository and transportation mechanisms' capacities.

364 Moringa Oleifera filler has an actual density of 0.98±0.74 g/cm3 and a porosity of 34.75±0.56 %,

16
365 respectively (Table 2). The true density is indeed more significant than that of Jatropha curcas seeds

366 [Bamgboye and Adebayo 2012], Fennel seeds [Shafiee et al. 2010], rice husk [Adebowale et al.

367 2010], and Capparis ssp. Fruit fibre [Sessiz et al. 2007] and lesser than that of Flax seed [Eissa

368 2009], corn husk [Chang et al. 1988] and mustard seeds [Grewal and Singh 2016]. The voids in seed

369 stock improve the volume while the mass remains equivalent, which leads to decreased bulk density

370 compared to actual density. Moringa Oleifera fillers' porosity is analogous to the Nigerian cowpea

371 [Kayode et al. 2018], Pigeon pea [Preethi et al. 2019], rice husk [Chang 1988], and Vigna

372 radiate green gramme [Pandiselvam et al. 2017]. It should be observed that the permeability of the

373 seed bulk affects the airway restriction amid the aeration and curing processes. The Moringa

374 Oleifera seed's angle of repose is 32.78±0.48 °. The significantly lower levels of repose and the form

375 of the particles appear to be the causes of the ease with which the seeds roll over one another [Della

376 and Siboni 2015, Mishra and Sinha 2020]

377 Table 1: Chemical compositions of the novel seeds/fibers/husks

Seed/fibers/husks Cellulose Hemicellulose Lignin Ash (%) Reference

(%) (%) (%)
TMCF 34.71±0.94 15.37±0.98 10.45±0.71 5.09±0.87 Present study
5% alkali treated 66.25±0.92 7.21±0.87 3.17±0.73 2.51±0.96
TMCF
10% alkali 50.41±0.83 11±0.97 8.93±0.75 4.85±0.97
treated TMCF
Moringa Oleifera 32±2 16±3 12±2 5±2 [Mishra and Sinha
seed 2021]
5% alkali treated 55±3 9±0.9 5±0.8 3±0.8
Moringa oleifera 43.44 0.25 45.54 10.42 [Nayak and Khuntia
pod fiber 2019]
5% alkali treated 67.12 0.11 24.57 7.7
Moringa Oleifera
pod fiber
Moringa Oleifera 5.59 4.46 6.49 13.2 [Mishra and Sinha
leave fiber 2020]
Acacia planifrons 73.1 9.41 12.04 4.06 [Senthamaraikannan
bark fibers et al. 2019]
5% alkali treated 79.13 3.08 7.41 3.10
Acacia planifrons
bark fibers
Cissus 82.73 7.96 11.27 - [Indran and Edwin
quadrangularis 2015]

17
 stem fiber
Coccinia grandis 63.22 - 24.42 - [Jebadurai et al.
stem fiber 2019]
Pennisetum 60.3 16 12.45 - [Ridzuan et al.
orientale fiber 2016]
5% alkali treated 66.7 10.3 8.7 -
Pennisetum
orientale fiber
Parthenium 51.5 9.7 14.3 4.7 [Binoj et al. 2018]
Hysterophorus
fiber
5% alkali treated 56.1 4.5 10.8 6.4
Parthenium
Hysterophorus
fiber
Switchgrass fiber 52.4±0.7 34.0±0.8 13±1 - [Enriquez et al.
5% alkali treated 70±2 15.3±0.8 14±1 - 2016]
Switchgrass fiber
Oil palm empty 36.7 35.8 18.6 - [Ching and Ng
fruit bunch fiber 2014]
Chlorite bleached 80.2 14.3 3.5 -
Oil palm empty
fruit bunch fiber
Tridax 32 6.8 3 - [Vijay et al. 2019]
procumbens fiber
5% alkali treated 45 3.6 2.3 -
Tridax
procumbens fiber
Brassica Naspus 48.5 29.0 20 6.6 [Hosseinpour et al.
rape seeds 2010]
Phoenix 23.9±0.1 26.8±0.1 21.6±0.1 - [Nabili et al. 2016]
Dactylifera L.
seeds
Prunus avium 23.10 37.90 31.67 1.31 [Cruz-Lopes et al.
Cherry seeds 2022]
Telfairia 20.30±0.7 38.60±0.2 1.4±0.2 15.30±0.2 [Amin et al. 2019]
Occidentalis fruit
fiber
Bauhinia 43.50±0.50 20±1 19.50±1.50 3.16±0.3 [Olugbenga et al.
monandra seeds 2019]
Jatropha seed 13.5 26.8 12.4 - [Shuhairi et al.
2015]
Sago seed shells 36.5±1 22.5±1 9.2±0.2 9.2±0.2 [Naduparambath et
al. 2016]
Chromolaena 12.03 10.76 6.33 5.60 [Fajobi et al. 2022]
odorata seeds
Jerusalem 20.95 5.48 5.05 5.15 [Tutt et al. 2013]
artichoke
378

18
379 Table 2: Physical properties of novel seeds/husks/fibers

Seeds/fibers/husks Bulk Actual Porosity Angle of Reference

density density (%) repose (ᴼ)
(g/cm3) (g/cm3)
Moringa Oleifera 0.79±0.34 0.98±0.74 34.75±0.56 32.78±0.48 Present study
seeds
Moringa Oleifera 0.247±0.05 0.510±0.02 58.86 17.834±0.3 [Deo and
seeds 8 5 51 Acharya 2010]
Nigella seeds 0.56±0.25 1.11±0.54 50 25.34±0.74 [Rokbi et al.
2011]
Salvia hispanica L. 0.722 1.009 28.2 16 [Abubakar and
chia seeds Benjamin
2018]
Jatropha curcas 0.43±0.24 0.85±0.43 50.37 36.45 [Singh et al.
seeds 2015]
White onion-1 seeds 0.639±0.00 1.187±0.02 46.22 39.34 [Ixtaina et al.
2 6 2008]
Arachis hypogaea L. 0.59±0.21 0.97±0.28 - 30.47 [Bamgboye
groundnut husk and Adebayo
2012]
Cotton seeds 0.575 - - 31.96 [Gajjar et al.
2019]
Fennel seeds 0.38±0.008 0.83±0.007 58.15 37.42 [Chukwu et al.
2018]
Soybean seeds 0.59 1.321 - 31.6 [Niranjan et al.
2020]
Flax seeds 0.663±0.00 1.243±0.00 46.65±0.2 27.6±0.5 [Shafiee et al.
3 9 2010]
Corn husk 1.25±0.27 1.42±0.53 13.3 - [Yang et al.
2017]
Nigerian cowpea 0.52 0.92 34.24 - [Eissa 2009]
Paddy rice husk 0.61 0.95 37.8 25.3 [Chang 1988]
Phaseolus vulgaris 0.51 0.81 30.7 11.8 [Kayode et al.
L. beans 2018]
Pigeon pea 0.85 1.324 36.45 24.52 [Adebowale et
al. 2010]
Daucus carota L. 0.357 1.020 64.96 32.79 [Eboibi and
carrot seeds Uguru 2018]
Litchi chinensis 0.577 1.202 52.02 - [Preethi et al.
litchi seeds 2019]
Wheat husk 0.795 1.390 42.8 36.7 [Gautam et al.
2016]
Capparis ssp. fruit 0.394 0.916 56.98 14.84 [Jalgaonkar et
fiber al. 2019]
Vignaradiata L. mug 0.99±0.03 - 38.73±4.31 - [El et al. 2009]
beans
Vigna radiate green 0.722±2.4 1.159±2.9 37.64±1.1 32.81±2.7 [Sessiz et al.
gram 2007]

19
 Mustard seeds 0.906 1.199 24.43 26.8 [Inekwe 2019]
Anise seeds 0.35 0.97 63.24 35.26 [Pandiselvam
et al. 2017]
Makhana 0.507±0.95 1.101±0.62 53.96±5.19 21.35±0.11 [Grewal and
Singh 2016]
Madhuca Longifolia 0.381 1.481 73.96 38.70 [Vishwakarma
seeds et al. 2015]
Helianthus Annuus 0.435 0.769 43.5 23.9 [Kumar et al.
L. sunflower seeds 2013]
380

381 Structural analysis of the TEMPO-modified nano-cellulosic filler (TMCF)

382 Figures 2 (a) show the FTIR spectra of untreated and alkali-treated TMCF. FTIR signifies the

383 presence of various functional groups exhibiting the material's complex behaviour. The intermediate

384 amide bond N-H stretch and the hydroxyl group (OH) cause the spectrum of filler to unify at 3412

385 cm-1. It is made up of components like proteins, cellulose, lipids, pectin, or lignin that are present in

386 the filler [Khalaf et al. 2018]. Because of the regular and irregular stretching of C-H and C-H2

387 linkages, the lipid content of seeds has a band at 2919 cm-1. Also, it states the existence of

388 hemicellulose and cellulose constituents in the seeds [Dalmis et al. 2020]. The peaks in the filler at

389 1712 cm-1 confirm the C=O bond of the carbonyl group. These exist in the seed filler due to the

390 addition of the epoxy polymer [Saa et al. 2019]. Peaks at 1408 cm-1, 1238 cm-1, and 1048 cm-1

391 ascribed to the C-N stretch of amide and N-H stretching. These peaks occur because of protein in the

392 seed [Sharma et al. 2021]. The peaks for filler modified with 5% alkali are largely similar to those of

393 untreated fillers, except for a decrease in intensity for the spectra at 3412 cm-1 and 1712 cm-1,

394 signifying the limited elimination of lignin and hemicellulose as a result of mercerization. Spectra

395 with centres at 2919, 1712, 1408 and 1238 cm-1 also dissipate in 10 % treated filler, indicating that

396 the elemental arrangement of the filler has degraded in response to the selective elimination of lignin

397 and hemicellulose, which is primarily to blame for the reduction in structural and mechanical

398 characteristics.

20
399 The XRD profile of untreated and treated TMCF are shown in Figure 2 (b). The broad intensity peak

400 is observed at 2Ɵ ̴21º, which indicates the 002 crystallographic planes of the cellulose lattice. The

401 crystallinity index of MOSF calculated using equation 4 is 43.21%. Similar outcomes of other

402 natural fibres like Sansevieria Ehrenbergii (52.27%) [Sathishkumar et al. 2013], Heteropogan

403 Contortus. (54.1%) [Singh et al. 2016], Acacia planifrons (51.72%) [Senthamaraikannan et al.

404 2019], Sida Rhombifolia (56.6%) [Gopinath et al. 2016], and Dichrostachys Cinerea (57.82%)

405 [Lavudi et al. 2018], etc. were found in the literature. It is generally known that the greater the

406 crystallinity, the more the mechanical strength, which results in better composite sheets. Therefore,

407 these results conclude that TMCF is significantly proportional to the novel natural fibres used

408 presently, and it can be used as a reinforcement in the polymer matrix. The C.I. of 5 % alkali

409 modified filler is 78.53 %. This increase results from the filler's non-crystalline lignin and

410 hemicellulose components beginning to be removed. The filler modified with alkali treatment had an

411 increased C.I. This is likely because the alkaloid completely reacts with the filler, removing all

412 pollutants and greasy and amorphous composition. Additionally, the crystalline fraction is

413 redistributed. It is observed that resulting from excessive delignification of the filler, which damages

414 the filler interface, there are no longer improvements in C.I. of 10% alkali modified filler [Mishra

415 and Sinha 2021].

21
416

417 Figure 2: FTIR spectra, b) XRD spectra for untreated and treated TMCF

418 The XPS investigation is used to characterize the surface chemical configuration. The basic

419 configuration and O/C proportion of the filler are shown in table 3. The substantial elements

420 observed in the filler are carbon and oxygen, recorded as 78.58% and 22.62%, respectively. The

421 minor elements identified are Si and nitrogen on the filler surface. To know the surface chemistry,

422 the oxygen to carbon ratio calculation is essential to analyze. Also, it provides knowledge about the

423 hydrophilic character of the filler. The lower value of the O/C ratio signifies the hydrophobic

424 character of the filler [Jebadurai and Raj 2019; Ridzuan et al. 2016]. The Oxygen-carbon proportion

425 showed in table 3 is 0.28, which is lower than most utilized natural fiber described by the researchers

426 like Centaurea solstitialis (0.54) [Keskin et al. 2020], jute fiber (0.46) [Bulut and Aksit 2013], hemp

427 (0.32) [Truss et al. 2016], luffa cylindrica (0.54) [Tanobe et al. 2005], kenaf (0.45) [Sgriccia et al.

428 2005]. MOSF is more hydrophobic than the traditional and novel natural fibres, commonly used for

429 composite medium reinforcement [Vijay et al. 2019].

430 Table 3: The atomic concentration (%) of the filler surface, according to XPS analysis

C O O/C Si N
MOSF 78.58 22.62 0.2870 0.99 1.76
431

22
432 Figure 3 (a-f) represents the high-resolution XPS spectrum of C1s and O1s peaks of untreated and

433 treated TMCF. The binding affinity, related bond type, and molecular concentrations are shown in

434 table 4. The composite materials are established as an outcome of covalent linkages between carbon

435 and oxygen elements. The C-C, C-O-C, C-O-C=0, and C-O-C bonds, as well as the peak positions

436 and weight concentrations, are shown in the untreated composites, as shown in figures 3 (a and d)

437 and table 4. Figures 3(b and e) show how the presence of 5% alkali-modified filler causes variations

438 in the strength of the carbon and oxygen connections. The growth rate is expected given that the 5%

439 alkali-treated seed filler has an increased quantity of carbon and oxygen in their chemical

440 arrangement, as evidenced by the minimal change in mass concentration in C-O-C=O and C-C from

441 0.3 atomic% to 0.6 atomic %. Beyond this period, the C-O-C=O is shown to have improved from

442 2.46 mass % to 3.91 mass %. The bond C-C and C-H connect to the alkali bond's interactions with

443 the cellulose present in the filler with considerable grafting response [Sgriccia et al. 2005; Nanda et

444 al. 2021; Sangian and Widjaja 2017; Liu and Hu 2008], consistent with those observed by Nicole et

445 al. in 2004. Similarly, the proportions of C-H and C-C connections decreased from 91.31 mass% to

446 86.25 mass % due to the excessive modification (10% w/v) of seed filler. The molecular network is

447 expected to get shorter than the 5% w/v treated filler gradually. Due to their unique properties, these

448 reduced molecular chains are constrained to improve mechanical interlocking [Pandiselvam et al.

449 2017]. Owing to the restricted enhancement, the mechanical properties of these fillers gets affected.

450 [Vijay et al. 2019]

23
451

452 Figure 3: XPS spectra showing the C1s and O1s peaks with different bonds.

453 Table 3: XPS peaks of C1s and O1s of treated and untreated filler with concentration level and

454 binding energy (eV)

Untreated filler 5% treated filler 10% treated filler

Bonds BE (eV) MCon (%) BE (eV) MCon (%) BE (eV) MCon (%)
C1s 283.52 91.2 283.86 94.84 283.50 91.10
O1s 531.24 5.73 531.64 5.92 531.17 3.87
C1s-C-H, C-C 283.48 87.21 283.82 91.31 283.41 86.25
C1s-C-O-C 285.24 3.14 285.49 3.27 285.20 2.88
O1s-C-O-C=O 532.18 2.46 531.31 3.91 532.12 2.14
O1s-C-O-C 531.12 1.83 531.54 1.51 531.10 1.18
455

456 Morphological analysis of TEMPO-modified nano-cellulosic filler (TMCF) and composites

457 Figures 4 and 5 (a-d), separately, display the SEM morphology and EDX spectroscopy of the treated

458 and untreated TMCF and their composites, respectively. The untreated filler shows a consistent and

459 glossy surface, as shown in Figure 4. The increased greasy, pectin and lignin constituents of the filler

24
460 may cause the above outcome. The waxes, pollutants, lignin, pectin and hemicellulose constituents

461 of the 5% alkali-treated TMCF (Figure 4) have been entirely or evenly removed, giving the

462 impression that it becomes rough. Exchanging the tension loading among them improves the

463 adhesive ability and enhances the filler's characteristics, which promotes the filler to matrix adhesion

464 [Naduparambath and Purushothaman 2016; Fajobi et al. 2022; Tutt et al. 2013]. Meanwhile, the filler

465 interface is observed to be impacted by 10% alkali dosage (fig 4), which leads to deterioration of the

466 filler surface and disruption to the surface and physical characteristics. The SEM micrograph of

467 TMCF-based epoxy composite sheets is shown in Figure 5 (a-d). Its superior structural union is

468 demonstrated by the autoclaved epoxy composite's appearance in figure 5 (a), which is a uniform,

469 polished and wavy-like structure with no cracks or breaks, similar to the findings of Wahyuningsih et

470 al. [Wahyuningsih et al. 2017]. Figure 5 (b) depicts the insertion of raw filler into the epoxy matrix

471 (b). The fillers may be seen on the epoxy surface, exhibiting poor adhesion qualities. The

472 hydrophobic feature of the filler, which results in pluck-away and fractures, is the reason that follows

473 the poor bond between the filler and epoxy [Jebadurai et al. 2019]. Relatively, the composites that

474 are 5 % mercerized (Figure 5 (c)) show regular filler evaluation and exhibit significant interfacial

475 adhesion among seed filler and epoxy composites. Fig. 5 (d) shows a 10% treated filler-based epoxy

476 matrix, and excessive mercerization can destroy the filler to matrix adhesion and induce

477 composites deterioration. This deterioration to the surface ultimately affects

478 the composite's decreased mechanical behaviour and the disappearance of functional groups in FTIR

479 spectra.

480 Figure 5 ((a), (b), and (c), (d)) shows the AFM images of autoclaved epoxy, untreated and treated

481 TMCF-epoxy composites. A consistent and clean texture with a mean roughness of 37.42 nm can be

482 seen for the neat epoxy composite. The layer of the composites becomes rougher with a mean

483 roughness of 50.24 nm when the untreated filler is incorporated into the epoxy matrix. Relatively, the

484 surfaces of the composite films subjected to 5% alkali treatment are significantly more rigid and

25
485 rough, measuring a mean roughness of 85.23 nm. This demonstrates complete molecular mixing of

486 seed filler, which eventually improves the interface relationship with the epoxy matrix. Meanwhile,

487 10% alkali-treated filler composites show lower roughness of 66.56 nm because of the damaged and

488 void-infused composites.

489

490 Figure 4: SEM image of untreated and treated TMCF

491

492

26
493

494 Figure 5: SEM images of a) autoclaved epoxy, b) untreated TMCF, c) 5% treated TMCF and d) 10%

495 treated TMCF -based epoxy composites.

496 Carboxylate content, zeta potential, degree of oxidation and polymerization

497 By oxidative treatment, large concentrations of carboxyl groups (2.25, 2.39 and 2.30 mmol COO/g

498 filler) were added to TMCF, which might create a negative charge to enable homogeneous

499 dispersion. By taking into account the electrostatic interactions among the carboxyl group, as

500 demonstrated by its zeta potentials, the durability of the TMCF solutions could also be explained

501 [108]. Intriguing surface charges of -50.90 mV, -55.92 and -52.64 mV were present in the TMCF, 5

502 wt. % TMCF and 10 wt. % TMCF, respectively. Viscosity was also used to gauge how oxidation

503 affected TMCF's polymerization rate (DP). Alkali treated TEMPO-modified nano-cellulose

504 fillers showed a low DP value, as indicated in Table 5, which was similar to previously published

505 results [Iyer and Jayaram 1971].

506 Table 5: Chemical characteristics of TMCF extracted from Moringa Oleifera

27
 Sample Zeta potential Carboxylate Degree of Degree of
(ζ)/(mV) content/(mmol oxidation (DO) polymerization
COO-/g filler) (DP)
TMCF -50.90 2.25 0.37 120.52
5% TMCF -55.92 2.39 0.42 115.36
10% TMCF -52.64 2.30 0.40 112.74
507

508 Static mechanical analysis of the TEMPO-modified nano-cellulosic filler (TMCF) composites

509 The mechanical strengths and modulus of the manufactured composites, as well as stress-strain

510 graphs for these variables with and without surface modification, is shown in fig 6 (a-d). The

511 maximum values for 5% treated seed filler reinforced composites' tensile and flexural strengths were

512 23.31 MPa and 75.47 MPa, respectively. This is explained by the enhanced interface connection

513 between the polymer and the reinforced material [Eissa 2009]. Micrographs (SEM) reveal layered

514 filler patterns in composites with a 5% treated TMCF that might have enhanced the interaction with

515 the epoxy. Furthermore, compared to autoclaved epoxy, the 10% treatment of the TMCF in the

516 composite sheet demonstrated the lowest tensile and flexural modulus (33% and 8%,

517 respectively). As depicted in fig 5 (d) of 10% treated TMCF-epoxy composites where the filler

518 aggregated, resulting in poor interlocking between the polymer and the filler. So, 5% of treated

519 composites show better mechanical properties and outperformed other composites and

520 autoclaved epoxy. These traits are similar to the epoxy composites made from wheat, flax, and maize

521 husk that use the same production techniques [Satapathy et al. 2009]. The bending stress

522 disfigurement stage, which enables composites to suffer irreversible alteration, follows the elastic

523 distortion, shown in the stress-strain curve (fig 6 (a and c)), and breaking happens as a result of

524 additional structural stretching. In particular, the tensile characteristics of composites are assessed as

525 the outcome of stress-intentional fracture. The tensile and flexural modulus graphs (fig. 6 (b and d))

526 demonstrated equivalent responses. The 5% treated composites increases surface characteristics,

527 promote homogenous filler dispersion throughout the entire matrix, and offer enhanced interfacial

528 interaction and composite strengthening. Filler-filler contact improved, as a result, ultimately

28
529 increasing the material's mechanical characteristics. Figure 7 shows the fractured surfaces after the

530 mechanical testing.

531

532 Figure 6: Tensile and flexural a) and c) stress-strain curve b) and d) strength and modulus of

533 untreated and treated TMCF -based epoxy composites.

534

29
535 Figure 7: SEM images of the fracture surface of untreated and treated TMCF -based epoxy

536 composites after tensile testing

537 Dynamic mechanical analysis of the TEMPO-modified nano-cellulosic filler (TMCF)

538 composites

539 Storage modulus: The capacity of a substance to retain given energy is determined by the storage

540 modulus (E′). It is associated with Elastic modulus, generating a composites rigidity [Fontes et al.

541 2021]. The influence of temperature on the storage modulus of 5% treated TMCF/epoxy composites

542 and neat epoxy composites with and without ageing is depicted in Fig. 8 (a). This temperature

543 adherence was investigated between 0 and 150 °C. The charts demonstrate that the storage

544 moduli reduce with increasing temperature for all samples. The graph shows that the 5% treated

545 TMCF-epoxy and untreated TMCF-epoxy composite exhibited the highest storage modulus values.

546 In the ranges of 0 to 80°C and 0 to 65°C, composites depict the glassy area. Similarly, there is a glass

547 transition phase between 63 and 79 ° C. and 80 – 98 °C. The rubbery phase similarly began at 98 and

548 79 ᴼC. and expanded to 150 ° C, respectively. However, the moduli of the autoclaved epoxy and all

549 composites fall as the temperature rises, and all specimens exhibit the maximum, middle, and least E′

550 values in the glassy, glass transition, and rubbery plateau sections, respectively. The composites'

551 complex molecular network constituents experience vibrational and, to a certain level, cyclic

552 oscillations in the glassy zone, which gives the composites a strength and higher storage

553 modulus (E′). The nano-molecular networks of composites undergo circular rotations in the glass

554 transition areas, and this momentum lowers the E′ of these materials. The nano-molecular links of all

555 the composites and autoclaved epoxy gain even more potential in the rubbery plateau section; as a

556 response, they also engage in translational movements, further reducing their storage modulus.

557 Significantly, higher E′ is observed in all three zones for composites composed of 5% treated

558 TMCF composites. Because of better interfacial contacts between TMCF nano-particles and matrix

559 epoxy.

30
560 Damping factor (tan δ): The tan δ vs. temperature graphs for untreated and treated TMCF-based

561 autoclaved epoxy is shown in Figure 8 (b). The peaks of each graph correspond to the material's Tg.

562 Tg is measured at 113.74°C for 5% treated TMCF-epoxy composites. Also, untreated TMCF showed

563 Tg values of 84.65°C. The autoclaved epoxy and 10% treated TMCF composites' Tg are 71.12 and

564 60.14°C lower than all other composites showing that they had little to no impact on the glass

565 transition temperature. This enhancement might be seen as a result of the 5% treatment

566 TMCF improved mechanical interlocking and interfacial interaction with the autoclaved

567 epoxy matrix. It was expected and discussed in the TGA section that filler tends to somewhat raise

568 the glass transition temperatures of the composites relative to the matrix by imposing certain limits

569 on the flexibility of the circumferential mobility of the nano-molecules.

570 Figure 8: Variation of a) storage modulus, b) Tan delta for untreated and treated TMCF-based epoxy

571 composites.

572 Thermogravimetric analysis of TEMPO-modified nano-cellulosic filler (TMCF) composites

573 Mechanism of degradation: Using TGA/DTG curves, the thermal properties of raw and treated

574 Moringa Oleifera filler-based epoxy composites were examined. The findings are shown in Fig. 9 (a

31
575 and b). The DTG and TGA plots are both displayed as temperature-dependent. Regardless of surface

576 modification treated, all composites eventually lose a little weight in the temperature range of 0 to

577 100 °C because of the water vaporization, which is also evident in the early slopes of DTG graphs

578 [Mangale et al. 2012; Joshi et al 1993]. For filler composites modified with alkali, the starting

579 temperature of deterioration is higher. The range for the initial phase of the decomposition processes

580 is 210 °C to 300 °C for untreated filler composites, and 300 °C to 410 °C and 240 °C to 290 °C for

581 5% and 10% treated filler composites, respectively [Mughal et al. 1999; Mangale et al. 2012]. A

582 comparable DTG graph is also presented in fig (9 (b)). Thermal stability has improved due to a slight

583 eradication of hemicellulose and the reduction of surface contaminants carried on by alkalization.

584 The deterioration of treated composites with 10% alkali begins at 205 °C, and the equivalent peak on

585 the DTG graph is shown at 250 °C. This damage may be caused by an overabundance of alkali,

586 which is destructive to the characteristics of the surface of the composite. The secondary peak is

587 indicated for untreated filler composite at 420 °C, whereas it is at 458 °C and 418 °C for 5% and

588 10% alkali-treated composites, respectively. These points represent the breakdown of cellulose and

589 lignin, respectively. For 5% mercerized composite, the least estimated weight is shown as a result of

590 optimal delignification, and this amount of treatment is the right one to increase the thermal stability

591 of the composite; any further increases in characteristics are negligible. The finding shows that filler

592 treated with 5% alkali is suitable for strengthening the epoxy matrix where processing temperatures

593 are lower than 300 °C.

594 Thermal stability: The reduced weight curves of 5% alkali-treated composite have shifted toward a

595 higher range of temperature, as shown in Fig. 9(a and b), indicating that the composites have

596 superior thermal characteristics to neat epoxy. Moreover, a 5% treatment shows reduced thermal

597 persistence than pure epoxy. According to this, composites' ability to withstand heat is boosted.

598 Composites with a higher cellulose concentration show better thermal endurance. Similar results are

599 observed in traditional fiber composites like sisal and rice husk [Fontes et al. 2021; Veerasimman et

32
600 al. 2021; Yang et al. 2021]. As a result, composite materials that are surface modified have higher

601 thermal efficiency.

602

603 Figure 9: TGA, b) DTG thermogram of untreated and treated TMCF -based epoxy composites

604 Kinetic modelling: The iso-conversational approaches were used to assess TGA evidence to

605 thoroughly recognize the thermal degradation kinetics of unmodified and alkali-modified Moringa

606 Oleifera seed filler-based epoxy composites. In order to determine the activation energy (Ea), the

607 graphs of the Friedman, modified Coats-Redfern (C-R), Broido, and Kissinger approach displayed a

608 typical pattern. Standard Friedman modelling graphs and linear regression instances for unmodified

609 and alkali-modified seed filler composites are shown in fig 10, 11, 12 and 13, respectively. These

610 figures show that the fitted lines are almost parallel, which suggests approximation of Ea at various

611 conversions and, as a result, indicates that the same reaction process may be possible (or the

612 consolidation of variable reaction process). As per the unfulfilled parallel line of conversion of 80%

613 in figures 10, 11, 12, and 13, the response mechanism may, perhaps, also vary at comparably

614 increased conversion times. As per earlier studies on cellulose [Veerasimman et al. 2021], the

615 complicated reactions in the deconstruction phase of the composite components may be the source of

33
616 the shift in the reaction process in greater conversions. This shift also increases the difficulty of

617 simulating the entire degradation process. According to the Friedman plot, for modifications of 20%-

618 50%, the activation energy estimates of untreated composites (fig 10 (a)) ranged from 92.12 kJ/mol

619 to 145.73 kJ/mol. Additionally, Ea values significantly improved as conversion rates reached 50%.

620 These findings suggested that the thermal degradation of untreated composites occurred through

621 various reaction pathways at different conversion rates. Oza et al., 2014 [Oza et al. 2014] noted a

622 parallel pattern. The differential thermal examination through the DTG trends might explain these

623 phenomena. If a heating rate of 10 °C/min is applied, the thermal degradation temperatures with

624 conversion rates of 20%-30% varied from 237 to 260 °C for untreated composites, with the DTG

625 curve temperature occurring at 310 °C, as shown in fig. 7 (b). Since holocellulose and lignin

626 underwent decomposition mainly between 211 and 310 °C and 310 and 520 °C, respectively. The

627 hemicellulose has almost entirely dissolved at the temperature range, while the lignin has remained

628 to disintegrate gradually [Yang et al. 2007]. In other terms, conversion beneath 20% is

629 predominantly caused by hemicellulose and lignin, and when conversion increased, so did their

630 respective quantities. The Ea of lignocellulosic content were also estimated to be 98-115, 200-220,

631 and 25-55 kJ/mol for cellulose, hemicellulose, cellulose and lignin, respectively, by Gronli et al.,

632 2002 [Gronli et al. 2002] and Yao et al., 2008 [Yao et al. 2008]. Thus, when the conversion rate is

633 lower than 30%, untreated composite thermal breakdown tendencies are significantly different. On

634 the contrary, as shown in fig 9 (b), 5% alkali treated composites displayed 1st order responses in

635 20% and beyond 60% conversion rates. At a temperature range of 260-410 °C, the thermal

636 deterioration of 20–40% breakdown transitioned to a 2nd-order response. At 260 °C, the response is

637 associated with the breakdown of hemicellulose, and at 410 °C, it is connected to the breakdown of

638 certain cellulose and lignin structural components. As a result, these alterations were related to

639 composite stimulation since alkali treatment helped to speed up the reaction. When the reaction is

640 complete, the response often returns to its initial 1st- order activity. Thus, the activation energy

34
641 estimates for 5% and 10% alkali treated composites with conversions of 20%- 50% were 118.14–

642 178.86 kJ/mol and 83.21- 132.15 kJ/mol, respectively. The 10 % alkali-treated filler composite is

643 shown in Fig. 9(c), where the fitted lines are more deformed. The Ea estimates are decreased because

644 of the surface deterioration brought on by overtreatment of alkali concentration.

645 The Coats-Redfern and Broido plot (figure 11 and 12), where the Ea of 5% alkali treated increases

646 (~39%) until a heating rate of 10 OC/min compared to neat epoxy, yielded similar results. The lower

647 Ea showed that a slow degradation response could occur during the primary composition's early

648 phases of reaching equilibrium. It is important to note that the accelerated process may differ from

649 the initial stage, which is predominantly driven by the degradation of relatively low molecular

650 composition [Mohomane et al. 2017]. The slight variances for Ea indicate that the degradation

651 response (or inclusion of variable reaction mechanisms) for 5% treated seed filler composites

652 remains intact over the indicated conversion area. For composites in all techniques, the lesser Ea in

653 low conversions and the improved Ea in increased conversions may reflect different degradation

654 pathways during the process [Sahoo et al. 2020].

655 Figure 13 shows the linear graphs of ln (β/Tp2) vs 1/Tp for the treated and untreated seed filler

656 composites from the Kissinger technique. Even though Kissinger's method considers one particular

657 heating rate, it presents an unusual condition for determining Ea and might not reveal the overall

658 trend of Ea. The calculated Ea for 5% alkali treated filler epoxy composite is 170 kJ/mol, which

659 confirms the previous findings. Compared to the Kissinger method, Friedman and C-R exhibit higher

660 Ea, and the Broido method exhibit a moderate Ea. It has been observed that obtained results using

661 Kissinger's approach are generally lower than those obtained using the isoconversional process. The

662 reduced Ea estimates of 10% treated seed filler composites may be caused by severe delignification,

663 primitive cellulose depolymerization, or deterioration of the composite

664

35
665

666 Figure 10: Linear plots of ln (dx/dt) versus 1/T FWO method for a) autoclaved epoxy, b) untreated

667 TMCF composites, c) 5% treated TMCF composites, d) 10% treated TMCF composites, e)

668 Activation energy plot for different conversion values calculated by Friedman method

669

36
670

671 Figure 11: Linear plots of ln[-ln(1-α)/T2] versus 1/T for a) neat epoxy, b) untreated TMCF

672 composites, c) 5% treated TMCF composites, d) 10% treated TMCF composites, e) Activation

673 energy plot for different conversion values calculated by Coats-Redfern method

674

37
675

676 Figure 12: Linear plots of ln[ln(1-Y)] versus 1/T for a) autoclaved epoxy, b) untreated TMCF

677 composites, c) 5% treated TMCF composites, d) 10% treated TMCF composites e) Activation

678 energy plot for different conversion values calculated by Broido method

679

38
680 Figure 13: Linear plots of ln(β/Tp2) versus 1/T for a) autoclaved epoxy, b) untreated TMCF

681 composites, c) 5% treated TMCF composites, d) 10% treated TMCF composites e) Activation

682 energy plot for different conversion values calculated by the Kissinger method

683 Water Uptake of TEMPO-modified nano-cellulosic filler (TMCF) composites

684 The water uptake rate is an essential characterization for understanding the durability of composites.

685 To evaluate these composites in real-world scenarios, test sample sheets are submerged in various

686 water states: seawater (pH=8.2) and deionized water (pH=6.4). The water gaining profile of the

687 untreated and treated TMCF -based epoxy composites with variable filler content in deionized and

688 seawater for 192 hours are shown in Figure 14(a, b, c, and d). It is evident from the figure that the

689 weight gain of the sheets increases by increasing the immersion time for a specific period.

690 Afterwards, sheets will get saturated through moisture, and no more water absorption will occur.

691 Investigators stated that the water absorption rate decreases with the surface modification of fillers

692 [Amin et al. 2019]. On the other hand, untreated filler epoxy composite shows that the sheet has the

693 highest water absorption rate in both states of water. This is because of a) significant quantity of

694 filler and void which hold additional moisture [Shuhairi et al. 2015], b) finely powdered filler, which

695 chokes the pores, resulting in a lower water absorption rate [Naduparambath and Purushothaman

696 2016]. Also, the free OH groups of cellulose appear, which combines with the moisture and creates

697 strong hydrogen bond correlations. These results enhance the moisture sensitivity of the sheets

698 [Olugbenga et al. 2019]. It also demonstrates that as the soaking period increased, the proportion of

699 water gained reduced. This is due to capillary absorption activity, in which liquid disperses into the

700 filler until it exceeds the threshold soaking, and the wetting of filler composites, which determine the

701 primary and secondary absorption stages that influence absorption. The hydrophilic feature of

702 cellulosic fillers causes a reduction in water uptake. At the same time, the soaking period increases

703 because the high amount of liquid molecules enter the composites' microcracks, causing the sheet to

704 expand and ultimately fracture [Chukwu et al. 2018; Niranjan et al. 2020; Shafiee et al. 2010]. Figure

39
705 14 illustrate how alkali modification affected the ability of TMCF-based epoxy composites to absorb

706 water. It demonstrates that ' capacity to absorb water is reduced by alkali treatment as the hydrophilic

707 characteristics of hydroxyl group decrease after the reaction with NaOH, filler surface turns into

708 hydrophobic. Also, after the modification, it removes the greasy and sticky components from the raw

709 filler; ultimately, the water uptake is reduced. Moreover, the 10% treated composite sheet increased

710 the water uptake rate, possibly because the excessive modification partially caused cellulose to

711 dissolve [Adebowale et al. 2010]. The reduction of α-cellulose causes the composite sheet to absorb

712 water [Shashikumar et al. 2018]. The considerable elimination of cellulose caused by the alkalization

713 increases the accessibility of the water uptake, which reduces the surface functionalities. The water

714 absorption rate of untreated and treated TMCF-epoxy composite immersed in saline water is lower

715 than in distilled water, as shown in figure 14 (a, c). This is because salt particles reduce the activity

716 of water molecules on the sheet's surface, leading to the admittance of salt molecules that hinder

717 water absorption [Fajobi et al. 2022]. The thickness swelling rate of untreated and treated TMCF-

718 epoxy composites at two water states with increasing immersion time are shown in figure 14 (b, d). It

719 is evident that the swelling rate is reduced by surface modification, similar to water absorption.

720 Therefore, 10% of treated composite sheets in distilled, and saline water have the second highest

721 swelling rate, which is 67% and 68%, respectively. When the TMCF-epoxy composite sheet is

722 immersed in two water states, the capillary travail among micro-cracks and the fillers' hydrophilic

723 nature is the principal source of water absorption that enhances the thickness of the composite

724 sample [Tutt et al. 2013].

40
725

726 Figure 14: a) and c) Water uptake rate, b) and d) Thickness swelling % of composites during 192 h

727 of immersion time in distilled and saline water states for untreated and treated TMCF -based epoxy

728 composites

729 Static and dynamic contact angle analysis of TEMPO-modified nano-cellulosic filler (TMCF)

730 composites

731 The wettability theory provides the reaction on the composite surface and is extensively researched

732 for practical implementation, such as self-purifying or shielding compounds [Symington et al. 2009].

733 The water contact angle, which relates to the degree of droplet dispersion on the material surface,

41
734 determines the wettability potential. Table 6 displays the contact angle of different liquids estimates

735 for neat epoxy and treated and untreated TMCF-based epoxy composites. Figure 15(a) illustrates the

736 surface energy phenomenon for all the composites with millipore water. For instance, if the contact

737 area is smaller, the surface energy on the polymeric surface, where the dimension of the liquid

738 droplet is more critical, can be denoted as providing a more extensive wettability capability; this is

739 known as a hydrophilic material. Similarly, if the contact area is higher than 90˚, composites hold the

740 potential to resist liquid. The surface energy of composites is calculated using SurfTen software

741 (Make: Claudio; Series: 4.3), which implies the Van Oss technique [Arshad et al. 2021]. Neat epoxy

742 has a 78.4° contact angle and demonstrates hydrophilic characteristics. The untreated TMCF-loaded

743 epoxy composite increased surface energy and water contact angle by 10%. According to the

744 hypothesis, surface modification of the filler-loaded composites increased the cellulose content,

745 which increased the crystalline structure of the filler and produced a compacted specimen that

746 increased the contact angle and delivered decreased adhesive strain when interacting with the liquid

747 droplet cohesion capacity levels. Due to the uniform distribution of nano-cellulose filer in the

748 composite structures, TMCF-epoxy composite has less hydrophilicity than autoclaved epoxy

749 materials. Similar outcomes have been reported for epoxy composites made from banana/pineapple-

750 and basalt-fibre by Arshad et al. in 2021 [Arshad et al. 2021] and Atmakuri et al. in 2020 [Atmakuri

751 et al. in 2020].

752 The Wilhelmy equation was used to evaluate the dynamic contact angles of 5% treated TMCF-based

753 epoxy composites in water and ethylene glycol at various assessment rates ranging from 500 m/s to

754 8000 m/s. According to the findings, all sample liquids' advancing angles rely on angle speed

755 dependency. In water and ethylene glycol; the angles range from 65° to 98° and 53° to 82°,

756 respectively (fig. 14 (b)). The investigation of Blake [Berg 1993] also revealed similar results.

757

42
758 Table 6: Contact angle analysis of different liquids on composites with and without surface

759 modification

Composites Millipore water Ethylene glycol References

Autoclaved epoxy 78.4±0.23 72.4±0.38 Present study
TMCF 86.2±0.41 75.2±0.67
5% treated TMCF 92.2±0.32 90.7±0.19
10% treated TMCF 81.6±0.24 71.9±0.34
Carbon fiber 55.80 32.99 [Luo et al.
2011]
Coir fiber 72.8 39.0 [Tran et al.
2011]
PLLA microfibers 110.45 - [Zhou et al.
2015]
PVC/PVP nanofiber 135.70 - [Asmatulu et
al. 2013]
Aramid fiber/epoxy 54.23 - [Hao et al.
2012]
Pulp fiber unbleached 33.14 - [Jin et al.
2022]
Typha fiber/epoxy 60.12 - [Rizal et al.
5% treated Typha fiber/epoxy 83.12 - 2019]
Zmioculus Zamiifolia fiber 70.6 - [Tengsuthiwat
5% treated Zmioculus 77.2 - et al. 2022]
Zamiifolia fiber
760

761

762

763

43
764 Figure 15: a) Surface energy with contact angles of all the untreated and treated TMCF -based epoxy

765 composites, b) Dynamic contact angles of all the untreated and treated TMCF -based epoxy

766 composites with two different liquids

767

768 Conclusion

769 The present study focused on fabricating autoclaved epoxy composite with reinforcing novel and

770 economical TEMPO-modified nano-cellulosic filler (TMCF). The surface treatment of TMCF

771 composites was subjected to UTM, FTIR, SEM, XRD, AFM, XPS, TGA, water uptake and static and

772 dynamic contact angles for better and comparable properties with autoclaved epoxy and untreated

773 seed filler composite. The 5% treated TMCF composite proved to have the highest tensile and

774 flexural strength, i.e., 23.31 MPa and 75.47 MPa, respectively. The XPS results of TMCF showed

775 C–C or C–H and O=C groups and hydrophobic qualities as per the O/C ratio (0.28). The water

776 absorption and thickness swelling rate of 5% treated TMCF-epoxy composite decrease by ~12%. In

777 distilled water, the swelling rate increased by 6%, whereas in the saline water state, 5.2% increment

778 was reported for 5% treated filler composite material. Also, 5% treated filler composites displayed a

779 contact angle of >90ᴼ according to measurement investigation, showing that the 5% of treated

780 composites turn hydrophobic in nature. This results from the cellulosic material's increased ability to

781 uptake liquids, which causes dimensional, topological, and mechanical alterations in the composite.

782 Four different isoconventional methods (Integral and differential) were used to analyze thermal

783 deterioration and activation energy for TMCF/epoxy composites, and the results showed comparable

784 tendencies. However, there are slight deviations due to the presumptions throughout the model

785 building. A reduction in activation energy accompanied the sequence of Friedman>Coats-

786 Redfern>Broido>Kissinger. Finally, it can be concluded that 5% treatment of alkali in combination

787 of TEMPO-modification can be an excellent alternative to synthetic fibres and traditional natural

788 fibres and can be built easily with epoxy polymers for semi-structural applications.

44
789 Authors Contribution

790 Authors 1 and 2 both have conceived the ideas and experimental design of the research work. The

791 primary author has performed the experiments, data collection and interpretation and drafted the

792 paper. The secondary author has reviewed the scientific contents and stylistic revisions to the

793 manuscript.

794 Declaration of competing interest

795 The authors declare that they have no known competing financial interests or personal relationships

796 that could have appeared to influence the work reported in this paper.

797 Data availability

798 Data will be made available on request.

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Declaration of Interest Statement

Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.