Accepted Manuscript

Investigation of mechanical, thermal and water absorption properties of flax

fibre reinforced epoxy composite with nano TiO2 addition

Vishnu Prasad, M.A. Joseph, K. Sekar

PII: S1359-835X(18)30389-0
DOI: https://doi.org/10.1016/j.compositesa.2018.09.031
Reference: JCOMA 5200

To appear in: Composites: Part A

Received Date: 16 May 2018

Revised Date: 30 August 2018
Accepted Date: 30 September 2018

Please cite this article as: Prasad, V., Joseph, M.A., Sekar, K., Investigation of mechanical, thermal and water
absorption properties of flax fibre reinforced epoxy composite with nano TiO2 addition, Composites: Part A (2018),
doi: https://doi.org/10.1016/j.compositesa.2018.09.031

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 Investigation of mechanical, thermal and water absorption
properties of flax fibre reinforced epoxy composite with nano TiO2
addition
Vishnu Prasada,*, M.A. Josepha, K. Sekara
a
Department of Mechanical Engineering, National Institute of Technology, Calicut-673601, India

Abstract

The present study aims at exploring the influence of nano TiO2 in enhancing the mechanical, thermal and

water absorption properties of the flax fibre reinforced epoxy composites. The composites were prepared using the

compression moulding technique. Epoxy was modified using nano titanium dioxide (50 nm size) at a loading rate

(percentage by weight of the composite) of 0%, 0.5%, 0.7% and 0.9% by mechanical stirring and sonication process.

The morphological characterisation was done by Scanning electron microscopy and the structural properties by

Fourier transform infrared spectroscopy. The results indicate a significant improvement in strength of the composite

system with the addition of TiO2. The optimum weight percentage for maximum performance was obtained as 0.7.

The increase in tensile, flexural, impact and interlaminar shear strength values were observed as 10.95%, 20.05%,

10.45% and 18.80% respectively. Water diffusion coefficient was reduced by 31.66% by the addition of nano

particles.

Keywords: A. Biocomposite, A. Natural fibres, B. Mechanical properties, E. Compression moulding

* Corresponding author. Tel.: +91 9745814385.

E-mail address: [email protected]

1. Introduction

The environmental sustainability issues related to synthetic products have driven researchers to focus more

on natural products in the field of engineering applications. Natural fibre reinforced composites have emerged as a

powerful platform and centre of attraction in composite research. Unlike synthetic fibres, the carbon dioxide cycle of

natural fibres is nearly closed when they are disposed. This is because the carbon dioxide, which was absorbed by

the plant before, is emitted back [1]. Awareness on greener and safe environment boosted, and led way in selecting

natural fibres as reinforcement for composite materials. Hence they are categorized under sustainable materials.
Natural fibres such as jute, coir, kenaf, sisal, flax are commonly used as reinforcements. Among them, flax fibres are

known for their highest tensile strength [2–4]. Flax fibre when compared with glass fibres have as appreciable

specific strength (1300 vs1350MPa/gcm-3) and specific modulus (20-70 Vs 30 GPa/gcm-3)values [5,6]. The common

issues faced by natural fibre composites are poor interfacial bonding, wetting, thermal properties and anisotropic

behaviour [7–9]. Thus the use of natural fibre composites for load bearing applications are limited. This led

researchers to focus on the development of natural fibre composite by matrix and fibre modification techniques. The

reason for poor mechanical properties of natural fibre reinforced epoxy composites is mainly due to their poor

interfacial bonding formed between hydrophilic fibre reinforcement and hydrophobic thermoset resin (epoxy) [10].

Several attempts have been made in order to improve the affinity and adhesion between the fibre reinforcement and

matrix. Among them are the fibre treatment, grafting of fibres with nano fillers and matrix modification with the

addition of nano fillers. A number of studies have shown that fibre treatment (alkali treatment) of flax fibre

reinforced epoxy composites showed improvement in the tensile properties by improved interface bonding [11,12].

Chemical modifications remove lignin, hemicellulose, wax and other impurities from the fibre surface making their

surface topography rougher which aids in improving the mechanical interlocking between the fibre and matrix

[13,14]. Fibre modification by grafting of flax fibre with nano TiO2 was reported with an improvement in tensile

strength and interfacial shear strength by 23.1% and 40.5% respectively. The presence of nano particles in the

surface enhanced the mechanical properties of the composites by connecting the fibre and matrix efficiently [15]. So

far very little attention has been paid on grafting of nanoparticles on natural fibres for composite development.

Similarly, there is relatively small body of literature that is concerned with matrix modification of natural fibre

composites. Pure epoxy has inherent brittle fracture behaviour and poor crack propagation resistance which in turn

limits them from eminent applications [16]. Thus epoxy modification is advised with the addition of nanofillers to

suitably increase the properties. The nanofillers commonly used are oil palm fillers, nanocellulose, nanoclay, nano

silica etc. Nanoscale fillers are added to the polymer matrix system to upsurge its mechanical properties in order to

meet the demand set by the industries and procedural applications. The nanofillers have specific characteristics that

will improve the mechanical, electrical, thermal and magnetic properties of the composite system [17,18]. Better
2
dispersion of nano fillers in the matrix improves the fibre matrix interface bonding which helps in transferring load

from fibre to matrix. Few studies have evaluated the matrix modification of epoxy resin with various nano particles

such as metal oxide particles, nano clay, nano cellulose etc. out of which TiO2 filled epoxy composite showed

appreciable improvement in the tensile and flexural properties [19].

The nanofiller with its large surface area connects the reinforcement and matrix formulating a better bond.

This also helps in shifting the stress concentration from the matrix to the load bearing reinforcement, thereby

delaying the fracture [17]. The present study selected nano titanium dioxide as the nanofiller for epoxy matrix

modification. Titanium dioxide is a naturally occurring oxide on titanium, which grabbed its attention due to its

highlighting properties such as mechanical, structural, anticorrosive, dielectric, and good compatibility with other

materials [20]. Nano titanium dioxide, due to its low fabrication cost, better availability and notable mechanical and

thermal properties can be used as better filler in epoxy composites. Thus, this study is set out to inspect the outcome

of matrix modification through nano TiO2 addition on the epoxy composite with flax reinforcement, on its thermal

and mechanical properties such as tensile, flexural and impact. Morphological characterization is performed on the

tensile fractured surface to analyze the contribution of nano TiO2 at the fibre matrix interface.

2. Experimental

2.1. Materials used

Flax fibres in the form of balanced satin weave 0°/90° with average thickness 0.7mm and areal

weight 200gsm were used as the reinforcement material (BComp Ltd. Switzerland). The 4H satin weave is

characterized by four weft yarn floating over warp yarn or vice versa. The matrix materials used for the study are

Epofine 556 (Epoxy) and Finehard 1926 (hardener). A releasing agent (Finelube SI 01) for easy removal of the

fabricated composite from the mold was also employed. The matrix materials were obtained from Fine finish

organics Pvt. Ltd, India. Nano titanium dioxides were purchased from Kerala Minerals and Metals Ltd, India. Table

1 enlists the properties of the materials used.

3
2.2 Composite preparation

Flax fibres were washed with deionized water to remove dirt or any foreign particles and then dried in hot

air oven at 100°C for 8 hours to remove the moisture content. Four layers of flax fibres were selected and the

volume fractions of fibres were maintained at 28 percentage [21,22]. Epoxy and hardener were mixed in ratio

100:60 as recommended by the matrix manufacturer. Releasing agents were applied to the mold for easy removal of

the composite laminates. Composite was fabricated by placing 4 layers of flax fabric plies one by one on mold plate.

Each plies was uniformly coated with epoxy resin ensuring proper wetting. The mold was then placed in the

compression moulding machine at a uniform pressure of 5MPa and at a temperature 100°C for 30minutes. Fig. 1

illustrates the schematic diagram of compression moulding process. Flax fibre reinforced epoxy composite was thus

prepared. Later, for the matrix modified composite samples, nano titanium dioxide of 50 nm size was introduced

into the matrix system at varying weight percentage i.e. 0.5 %, 0.7 % and 0.9 %. The weighed nano TiO2 were

mixed to the epoxy using a mechanical stirrer at 1000 rpm for 60 minutes followed by sonication process for

45minutes. The combined processes will confirm good dispersion of nanofillers in the matrix [23,24]. All samples

were subjected to two-stage post curing as recommended by the matrix manufacturer. The curing cycles were 80°C

for four hours and 120°C for two hours. Finally, the specimens were prepared for the individual mechanical testing

according to the ASTM standards.

2.3 Characterization

2.3.1 Mechanical characterization

Mechanical testing was conducted on the flax fibre reinforced composite and TiO2 filled flax fibre

composites to evaluate the influence on matrix modification on the corresponding studies. The tensile properties of

composites were assessed using Shimadzu AG-X plus UTM. The samples were prepared according to ASTM

D3039-14 standard with dimensions 250 mm in length, 25 mm in width and 3 mm in thickness. A constant

crosshead speed of 1mm/min was followed for all the samples.Three point bending test was conducted on the

prepared composite samples according to ASTM D7264-15 standard in Shimadzu AGX-S model. The thickness of

4
the sample was 3 mm with a span to depth ratio 32:1 and at a crosshead speed of 1mm/min. The impact strength of

the samples were analyzed using Zwick Roell HIT25P apparatus according to the ASTM D256-10 standard. The

impact velocity for the test was 3.4581 m/s. Interlaminar shear strength (ILSS) was studied using short beam shear

(SBS) method according to ASTM D2344-16 standard. ILSS uses a three point bending test set up with span to

thickness ratio (4:1). The tests were conducted in Shimadzu AGX-S model with a crosshead speed of 1mm/min. The

specimen dimension was 18mm (length) x6mm (width) x3mm (thickness).

2.3.2 Thermal characterisation

Thermal stability of the composites were examined by performing thermogravimetric analysis (TGA). This

test method computes the weight loss incurred in the materials with the action of temperature in a controlled

atmosphere. Measurements were made by subjecting the material to a temperature range of 25°C to 700°C in an

atmosphere of nitrogen gas (ASTM E 1868). TGA was conducted using Hitachi Thermal analysis system Model

STA7200 with a gas flow rate of 120 mL/min and specimen weight of 10 mg. Differential scanning calorimetry

(DSC) analysis was conducted to study the thermal properties of the samples. The tests were performed in DSC Q20

TA instrument at a heating rate of 10° C/min in a nitrogen atmosphere. The gas flow rate was maintained at 50

mL/min. Flax fibre reinforced samples and matrix modified samples with nano TiO2 addition were analysed under

DSC test condition to infer about the glass transition temperature (T g). Understanding the Tg is essential to know

about the reliability and sustainability of the mechanical properties at its service temperature.

2.3.3 Scanning electron microscopy

Scanning electron microscopy (SEM) was conducted on the tensile fractured surface to analyse the effect

of nano TiO2 particles in the matrix modification. Studies were performed with a Zeiss Neon40 scanning electron

microscope. The instrument was functioned at an acceleration voltage of 2.0 kV with 8.8mm working distance. The

5
fractured surface was coated with 4 nm thin layer of uniform gold coating using Quorum Q150T ES equipment and

cooled before conducting the study

2.3.3 X-ray diffraction analysis (XRD)

Nano TiO2 powder was characterised using Rigaku Miniflex 600 diffractometer. The Cu Kα source

radiation with λ=1.54 Å was operated at a voltage of 20kV and current 2mA. The scan range (2 θ) was selected

between 3-90°, with a scan speed of 2°/min.

2.3.4 Fourier transform infrared spectroscopy (FTIR)

The FTIR spectrum was analyzed using Cary 630 FTIR instrument with spectra range from 4000 cm −1 to

650 cm−1 at room temperature.

2.4 Water absorption study

Water absorption tests were conducted on the composite samples according to ASTM D570-10 standard.

The length, width and thickness of samples were 76.2mm, 25.4mm and 3mm respectively. The edges were polished

and made smooth to avoid any crack. Before conducting the test, samples were dried in hot air oven at 50°C for 5

hours to remove any moisture present in the sample. The samples were then immersed in deionized water at room

temperature and were periodically removed from the water, dried with absorbent paper and weighed to nearest

0.0001g. Weight gain during water absorption test in percentage was calculated using Eq. (1), where mo is the initial

weight, m is the weight at the instant of measurement and Wt is the weight gain percentage.

(1)

6
3. Results and discussions

3.1. Morphology of nano TiO2 particles

The morphology of nano TiO2 particles was studied using Zeiss Neon40 Scanning electron microscope

(SEM). Fig. 2(a) illustrates the size and shape of nano TiO2 particles. It is noted that the shape of nano particle is

spherical with average size 50nm. X-ray diffraction (XRD) analysis was conducted to identify the crystalline nature

and phase of nano TiO2 particles using Rigaku MiniFlex 600 equipment. Fig. 2(b) explains the diffraction peaks in

the XRD pattern at various diffraction angles (27°, 36° and 55°). The results indicate the presence of rutile phase in

nano titanium dioxide particles. The peak value from XRD results are in good agreement with standard spectra of

JCPDS data (number 88-1175 and 84-1286) confirming the rutile phase of TiO2 nanoparticles [25]. The XRD results

showing the purity of nano particle is good. Nano TiO2 was mixed in epoxy resin by mechanical stirring and

sonication process. SEM image illustrated in fig. 3 (a-b) mentions the proper dispersion of nano particles in 0.7wt %

TiO2 epoxy samples. For samples with higher weight fraction of nano particles in the matrix (i.e. 0.9wt % TiO2

epoxy samples) showed the presence of agglomerations.

3.2 Tensile test

The tensile studies were conducted on the flax fibre composite and TiO2 filled flax fibre composite samples

to understand the tensile properties and assess the contribution made by the nano titanium dioxide particles. The

optimum weight ratios in the matrix were evaluated based on the better tensile strength values. The results imply

that 0.7 wt% TiO2 added epoxy composite with flax fibre as reinforcement yielded maximum tensile strength values.

It is evident that the contribution of nano TiO2 particles has made the composite tougher and stiffer. Fig. 4(a)-(c)

illustrates the tensile strength, tensile modulus and percentage elongation values of composite samples with varying

nano TiO2 addition in the matrix. The percentage increase in tensile strength with the addition of 0.7 wt% TiO2 in

the flax fibre composite was 10.95% (78.85 MPa) when compared to flax fibre reinforced composites without nano

TiO2 addition (71.06 MPa). The significant enhancement in the tensile strength of the composite is mainly due to the

7
improved dispersion of nano TiO2 in the matrix attained by the combined action of mechanical stirring and

sonication, which results in an increased bonding between the matrix and the fibre. The larger surface area of

nanoparticles enables better connection between matrix and fibre interface, which aids in transferring the stress,

thereby delaying the crack propagation resulting in enriched mechanical properties. Further addition of

nanoparticles in the matrix beyond 0.7 wt% TiO2 is found to have a reduction in the tensile strength values. The

trend beyond this point follows a declining path when more nanoparticle is added to the composite. Increase in nano

TiO2 content in the matrix leads way for particle-particle interaction to be dominating rather than availing the

nanoparticles to interact with the fibre matrix interface. With the increase in nanoparticle content in the matrix, Van

der Waal’s force is developed within them, triggering the agglomeration of particles, which results in poor

dispersion in matrix [26]. The active surface area of the nanoparticle which should act as a bond between fibre and

matrix gets reduced, further relegating the chance of load transfer from matrix to fibre. This in turns results in poor

tensile strength values. This also leads to the formation of voids in the matrix making them hotspots for crack

initiation and failure. The tensile modulus value is found to be increasing with the increase in nano TiO2 content in

the matrix. The effect of stress concentration is relieved when a low deformation property is studied [27,28]. The

maximum value of tensile modulus was obtained as 2.2748GPa for 0.9 wt% TiO2 samples. The improvement in the

tensile modulus was a result of the increase in load bearing capacity of the composites, with the addition of nano

fillers. Trend in tensile strength and modulus followed the same pattern, similar cases were reported for nano filler

added composite samples [29]. On the other hand percentage elongation value was found to be decreasing with

increase in nano TiO2 content in the flax fibre composite. The addition of nano fillers in the matrix makes the

composite much stiffer and rigid which limits the plastic deformation during deformation.

3.3 SEM observation on tensile fracture surface

Tensile fractured surfaces were analyzed to evaluate the fibre matrix interface bonding and the fibre failure

using SEM. Fig. 5 and Fig. 6 indicate the fractured surface of the various flax fibre reinforced composite sample

8
with TiO2 addition in matrix from 0wt% to 0.9wt%. It can be perceived that the fibre matrix interface bonding

reflects highly on the strength of the composites. From Fig. 5(a) and 6(a) it is evident that the fibre matrix interface

in the case of flax fibre epoxy composites with 0 wt % TiO2 in matrix shows poor bonding, which results in the

minimum strength of the composite. Severe fibre pull out were observed in this case due to poor fibre matrix

interface. Fig. 5(b-d) and Fig. 6(b-d) reveals that the addition of nano TiO2 in the matrix shows an improvement in

the interface bonding of fibre and matrix. Improvement in fibre matrix bonding was observed in case of 0.5 wt% and

0.7wt % of TiO2 in the matrix. Reduced fibre pull out observed in these cases is a result of better bonding between

fibre and matrix. This helps in transferring the load from the matrix to fibre inducing fibre failure, thereby increasing

the maximum load at break. Nano TiO2 with its large surface area and being chemically active creates a good bond

between fibre and matrix. Mechanical interlocking formed between the fibre and matrix by the addition of nano

fillers aids to this interface development [30]. Better compatibility of nano TiO2 with polymer matrix influences the

interface positively. Further increase in weight percentage of nano titanium dioxide in epoxy beyond 0.7 wt%,

possibly increases the cluster size of particles resulting in poor dispersion [26,31]. In a detailed study conducted by

Goyat et al. [32], they showed that, as the addition of nano TiO2 in epoxy composite increases, the cluster formation

increases. Fig. 5(d) shows the fractured surface of 0.9 wt % added flax fibre reinforced composites spotted few

regions of fibre pull out. This is due to the increase in cluster formation of nano TiO2 particles at a relatively higher

weight percentage. This restricts the interaction of nanoparticles to the fibre and matrix interface. At a higher weight

percentage, particle-particle interactions will be dominating, raising the chance for poor dispersion and inferior

bonding of fibre and matrix as illustrated in Fig. 6(d). This will increase the chances of fibre pull out and poor

mechanical strength of the composite. From the SEM analysis, it is evident that better interface bonding is observed

in flax fibre composites with 0.7 wt % of TiO2 with a minimum fibre pull out.

3.4 Flexural test

Three point bending test was conducted on the composite samples to investigate the influence of nano TiO2

particles in the matrix. Flexural failure mode was observed on the samples after attaining the maximum load. A

9
crack was formed on the outer (tensile surface) of the specimen. Fig. 7(a-c) describes the flexural strength, flexural

modulus and percentage elongation values of the samples examined. The matrix modification with the addition of

nano TiO2 particles enhanced the flexural strength value of the composites. This is due to the improved rigidity,

better interface area and improved stiffness of the added nano TiO2 particles which strongly contributed to the

improvement of the flexural strength. The load is thus effectively transferred from the matrix through the interface

to the fibre. This causes a delay in crack propagation and diverts them, thereby improving the flexural strength of

the composites. Significant improvement in the strength was noted in case of the 0.7 wt% TiO2 added flax epoxy

composite in contrast to the rest of the composite samples. This is attributed to the effectual diffusion of nano TiO2

within the epoxy matrix. A superior bonding is thus exhibited within the fibre and matrix without any cluster

formation. With the addition of 0.7 wt% TiO2 in the flax fibre composite, the flexural strength increases by 20.05%

(88.77 MPa) when compared to the flax fibre reinforced epoxy composites without matrix modification (73.94

MPa). The flexural modulus value was found to be increasing with increase in nano TiO2 content in the matrix. The

maximum value of flexural modulus was obtained as 5.11 GPa for 0.9 wt% TiO2 added flax fibre composite. With

the addition of nano TiO2 in the matrix, percentage elongation values were found to be decreasing. This is due to the

improved interaction of nano fillers and matric which resists the movement of polymer chain during loading [33].

The improvement in flexural properties can be attributed due to (i) better dispersion of nano fillers, which aids in the

improved interfacial interaction between the nano fillers, matrix and fibre (iii) nano fillers restricting the motion of

polymer molecules thereby causing interlocking.

3.5 Impact test

The impact strength of the samples were analyzed and compared to understand the importance of matrix

modification with TiO2 addition. Fig. 8 shows that the impact strength values also follow a similar trend with that of

tensile and flexural properties. The results deduce that 0.7 wt% TiO2 added composites gives higher impact strength

(7.8598 kJ/m2) with a percentage improvement of 10.45% when compared to flax fibre reinforced epoxy composites

10
without matrix modification (7.1157 kJ/m2). The nano TiO2 fillers with its superior stiffness improve the strength of

the composites by playing a vital role in the fibre matrix interface. Better bonding is developed between fibre and

matrix resulting in higher impact resistance.

3.6 Interlaminar shear strength (ILSS)

Interlaminar shear strength (ILSS) of the composite samples was studied to understand the influence of

matrix modification in the fibre matrix interface. Type of failure observed was shear failure mode. A similar trend in

results was observed for flexural and ILSS studies, the later precisely measures the interfacial interaction between

matrix and fibre [34]. Fig. 9 indicates that maximum value for interlaminar shear strength was obtained for 0.7wt %

TiO2 added flax fibre reinforced epoxy composite (17.12MPa) with a notable improvement of 18.80% when

compared to flax fibre composite without matrix modification. The results suggest an improvement in the

interlaminar shear strength values were observed with the addition of nano TiO2 particles in the flax fibre reinforced

composites. Nano filler addition in the matrix induces mechanical interlocking with the fibre and matrix, thereby

restricting the movement of the fillers within the matrix under the application of load [35]. Matrix modification by

the addition of nano TiO2 effectively improves the load transfer between fibre and matrix, as nano filler bridges the

fibre and matrix.

3.7 Fourier transform infrared spectroscopy (FTIR)

The presence of functional groups in the flax fibre reinforced epoxy composites and the evidence of nano

TiO2 particle addition in the matrix was analysed by Fourier transform infrared spectroscopy (FTIR). The tests were

conducted using Cary 630 FTIR instrument with spectra range from 4000 cm −1 to 650 cm−1. From the analysis, it

was possible to acquire the existence of chemical constituents present in the fibre reinforced composites. Peaks of

metal oxide are generally found in the range 400-950cm-1 and from the FTIR data of the analysed composites, peaks

found in this region will be assigned to Ti-O bonding which indicates the presence of titanium dioxide [36,37].

From fig. 10 it can be noted that the peak in range 690-900 cm-1 assigns to the C-H bending present in the epoxy

11
matrix. The fingerprint region with peak value 547 cm-1 and 693 cm-1 is indicated in Fig. 10, which explains the

presence of TiO2 in the matrix modified flax fibre reinforced epoxy composites. The variation in transmittance

percentage value in each combination represents the variation in the amount of TiO 2 content present in respective

samples. For the FTIR curves of 0.5%, 0.7% and 0.9 wt% TiO2 added flax composites, the peaks which denote the

presence of TiO2 shows a downshift in the transmittance percentage value, indicating the evidence for the increase

in TiO2 content for the respective combinations. For the matrix modified flax fibre composite samples with addition

of 0.5-0.9 wt% of TiO2 nano particles, a slight downshift in the transmittance percentage of the peak 3366 cm -1 is

noticed. This is due to the formation of hydrogen bond between the hydroxyl groups of both matrix and

nanoparticles. This attributes towards the O-H stretching of hydroxyl groups [32] indicating that the addition of

nano TiO2 in the matrix effectively crosslink with the O-H cellulose chains of fibre and matrix. The peak value

2959 cm-1 is detailed to the C-H stretching [36]. The variation in transmittance percentage for the matrix modified

composites is contributed by the response from the bonding formed between epoxy and cellulose hemicellulose

content in the fibre [38]. A similar response is noted for peaks at 1602 cm-1 and 1502 cm-1 corresponding to the

benzene ring of epoxy or C=C stretching of aromatic ring [39].

3.8 Thermal properties

3.8.1 Thermogravimetric analysis (TGA) and Derivative thermogravimetry (DTG)

Thermogravimetric analysis was performed to observe the thermal stability of the prepared composite

samples. The TGA curves (Fig. 11a) explain that the initial degradation occurs at a temperature range of 110-

120°C. This is due to the dehydration of physically and slackly bound moisture on the surface of the composite and

due to the presence of solvent in the polymer matrix. The volatile components such as moisture particles get usually

degraded at the initial mass loss curve. For a given fraction of weight, the samples that withstand higher temperature

are relatively more thermally stable. Further moving towards higher temperature, a major mass loss was observed at

382°C with a corresponding weight loss of 54.43% as illustrated in fig. 11a. This temperature is considered as the
12
maximum degradation temperature stating the materials thermal stability. Here the major mass of the composite is

lost due to degradation of epoxy and fibres. This is due to the degradation of aromatic group of epoxy resin and

cellulose and hemicellulose content in the fibres. The residues formed after this degradation took an elevated

temperature for succeeding degradation. The final degradation was observed at a temperature of 650 0C. No

significant variation in temperature was observed with the addition of nano TiO2 particles on the epoxy matrix of

flax reinforced composites. From the TGA results Derivative thermogravimetry (DTG) curves (Fig. 11b) were also

obtained. The peaks of DTG curve clearly illustrate the point at which the weight loss is more apparent or the

corresponding temperature at which thermal degradation on weight is maximum. DTG curve of various samples

shows that the temperature corresponding to major mass degradation occurs at 382°C. In this comparative study on

the influence on nano TiO2 being a filler in matrix system with flax fibre as reinforcement showed not much

difference in the temperature value of prominent mass degradation. The TGA curve or the thermal analysis in

general, illustrated the overall thermal stability of the composite system so that the maximum degradation

temperature of the sample could be inferred.

Results from earlier studies demonstrate that addition of nano TiO2 to epoxy composite can improve its

thermal stability by enhancing the cross link density of the polymer composite. Literatures suggest that thermal

stability of the epoxy matrix increases progressively by nano TiO2 addition up to 10wt %[18]. On the contrary

improvement in nano TiO2 content causes severe agglomeration which can result in poor mechanical properties. At

higher nano TiO2 content stress concentrations are generated due to agglomerated nano particles, causing crack

initiation and failure [31]. In the present study, the primary focus was to investigate the influence of matrix

modification on the mechanical properties. Further, thermal studies were conducted on the composite samples with

optimized nano TiO2 content (i.e. 0.5wt % to 0.9wt %) finalized from mechanical test results. As observed the

mechanical properties were found to be increasing relatively at a lower weight fraction of nano fillers (till 0.7wt %)

and a further increase in nano filler content (beyond 0.9wt %) resulted in reduction in the mechanical properties.

When thermal properties were evaluated in this range, nano TiO2 in the composite system were not sufficient

13
enough to enhance the thermal stability. Thus the addition of nano TiO2 in the matrix couldn’t generate any

highlighting influence on the thermal stability of the composite.

. The thermal stability results from the TGA analysis exhibits that the addition of nano TiO2 in the matrix

does not have any influence on the thermal stability of the composite. Though the thermal analysis results based on

the TGA and DTG did not produce an appreciable result by improving the thermal stability of nano TiO2 added flax

composites, the results can be inferred to find out the temperatures of maximum mass degradation.

3.8.2 Differential scanning calorimetry (DSC)

Thermal properties of the samples were studied using differential scanning calorimetry analysis. DSC

curves mentioned in Fig. 12.shows the heat flow vs temperature of the various samples. Glass transition temperature

(Tg) signifies the temperature range at which the thermosetting polymer changes from its amorphous state to a

flexible state. Tg generally provides the nature of polymer at its service temperature. Glass transition temperature is

obtained from the point of intersection of tangents drawn from the ends of endothermic peaks in the DSC curve [29].

They are drawn from the opposite sides of the dip in the curve. Here the endothermic dip is observed in the

temperature range 45°C to 80°C. The results conclude that 0.7 wt % TiO2 added composites provide a better glass

transition temperature of 69.52°C. Table 2 shows the glass transition temperature of composite samples.

Improvement in glass transition temperature for 0.7wt % TiO2 added composite is due to effective dispersion and

adhesion of nano TiO2 particles with matrix system. This, in turn, creates a better interaction with flax fibres,

confining the molecular mobility up to some degree [3,40]. Generally, in a thermosetting polymer with nanoparticle

addition, the factors that improve the Tg values are particle-matrix interface area, molecular weight and cross-linking

density. In this study, the addition of TiO2 nanoparticle in matrix generates a loss in the mobility of epoxy chain

segments resulting in a better interaction of nanoparticle with the fibre and matrix [41]. Better dispersion of nano

TiO2 particles in the matrix hinders the chain mobility thereby increasing the Tg value. When nano TiO2 particles are

added beyond 0.7 wt%, it causes poor dispersion in the matrix due to cluster formation, resulting in a decrease in the
14
Tg value. The matrix modification by the addition of 0.7wt % TiO2 in the composite improved the Tg value by 5°C,

indicating a slight improvement in the thermal property.

3.9 Water absorption

Water absorption is one of the important parameter which significantly degrade the mechanical properties

of fibre reinforced polymer composite materials. The hydrophilic nature of natural fibre is the reason why natural

fibres absorb water when they are exposed to moisture conditions. This causes the fibre to absorb water and swell,

which creates micro cracks in the fibre matrix interface. When water gets dispersed into the matrix or at the fibre

matrix interface, it will create a mismatch in the volumetric expansion of the matrix and fibre interface. This leads to

the development of localized stress and strain at various sections of composites. The absorbed water gets transferred

to other regions of the composite through capillary action. The water penetrates through the micro cracks to the fibre

matrix interface. The absorbed water expands the matrix, plasticizes it and cracks will be formed. This cause a

drastic reduction in the mechanical properties of the composite [42–44]. This phenomenon is a great drawback for

natural fibre reinforced composites. Hence, suitable measures should be taken to reduce this. This study reduces the

effect of water absorption and maintains the mechanical property of the composite by nano titanium dioxide

addition.

Fig. 13. illustrates the water absorption behavior of various flax fibre composite samples at different wt%

of TiO2 (0-0.9) in the matrix. The curves are plotted with the percentage of water absorbed as a function of square

root of time in hours. While studying the water absorption nature of polymer composites, it can be perceived that

water absorption is linear in the initial portion of the curve. The polymer satisfies Fick’s law of diffusion in this

region. Beyond this region, the absorption nearly gets saturated and later become ceased. Further increase in

absorption can be noted because of the degradation of matrix material and the moisture being penetrated via the

microcracks and due to capillary action. The water diffusion coefficient is calculated in Fickian diffusion range

using Eq. (2) [39,45].

15
 (2)

Where M1, M2 represents the percentage of water absorbed at time t 1 and t2 in the initial linear portion of

the curve. Mm denotes equilibrium water content and Dz symbolizes the diffusion coefficient. Taking into account

the dimensions of the sample subjected to water immersion, a modified diffusion constant D can be found out [26],

which is stated in Eq. (3). Where h, w and l signifies the thickness, width and length respectfully of the sample.

(3)

Flax fibre composites with matrix modified at 0.7 wt% TiO2 gave the best result for water absorption test

when compared to the other combinations. Water absorption coefficient is calculated from the linear portion of the

curve (assuming Fickian diffusion) using Eqs. (2) and (3). It can be perceived that the diffusion coefficient is

reduced by 31.66% for 0.7% nano TiO2 added flax fibre epoxy composite when compared to flax fibre epoxy

composite without nano TiO2 addition as shown in Fig. 14. It is perceived that addition of nano TiO2 in the matrix

condenses the water absorption affinity as compared to flax fibre composite without TiO2 addition in the matrix. The

reduction in water uptake of nano TiO2 added flax fibre composites is due to the development of effective interface

bond made by nano TiO2 with fibre and matrix. This reduces the affinity to absorb water through capillary action.

Conversely, while increasing the weight percentage of TiO2 in the matrix beyond a certain limit, there are chances

for the presence of entrapped voids in the composite samples. This is due to the agglomeration of nano TiO2

particles beyond a specific weight percentage and formation of voids during matrix modification generally observed

at a higher weight percentage of nanofillers [26].

4. Conclusions

The study was conducted to find out the significance of matrix modification of flax fibre reinforced

composites by addition of nano TiO2 in the matrix. The percentage by weight of nano TiO2 was varied as 0.5, 0.7

and 0.9. The optimum weight percentage for maximum performance was obtained as 0.7. The following conclusions

16
can be drawn:

 Remarkable improvement in the mechanical and water absorption properties was observed for the matrix

modified composite system. Homogenous and fine dispersion of nano TiO2 was attained with the combined

action of mechanical stirring and sonication process.

 The percentage increase in tensile, flexural, impact and interlaminar shear strength values for TiO2 added flax

composites were 10.95%, 20.05%, 10.45% and 18.80% respectively.

 Morphological images from SEM analysis shows the presence of minimum fibre pull out and better fibre matrix

interface bonding in case of flax fibre composites with TiO2 addition.

 FTIR analysis supports the incorporation of nano TiO2 filler in the epoxy matrix, which is definite from the

fingerprint region of the FTIR curves.

 Noticeable improvement in glass transition temperature was not achieved by the addition of nano TiO 2 in the

matrix. The increase in Tg value for 0.7 wt% added composite was by 5°C.

 It is observed that addition of nano TiO2 in the matrix reduces water absorption tendency. The diffusion

coefficient is reduced by 31.66% for nano TiO2 added flax fibre epoxy composite when compared to flax fibre

epoxy composite without nano TiO2 addition.

 Better diffusion of nanoparticles in the matrix develops a good fibre matrix interface, which aids in transferring

the stress, thereby delaying crack propagation. Improved rigidity and stiffness of the composite by addition of

nano TiO2 particles strongly contributed to the improvement of the properties.

Acknowledgment

The authors wish to thank National Institute of Technology, Calicut, India for facilitating to conduct the

preparation and testing of composite samples, also TEQIP-II for funding the project work. Authors wish to express

our thanks to Kerala Minerals and Metals Ltd, Kerala, India for supporting this research work by supplying Nano

17
Titanium dioxide. Support and guidance from Dr. Soney Varghese, Associate Professor, School of Nano Science

and Technology, NIT Calicut were really helpful and encouraging thorught this paper.

References

[1] Schmehl M, Müssig J, Schönfeld U, Von Buttlar H-B. Life Cycle Assessment on a Bus Body Component Based on Hemp Fiber and

PTP®. Journal of Polymers and the Environment 2008;16:51–60. doi:10.1007/s10924-008-0103-x.

[2] Koronis G, Silva A, Fontul M. Green composites: A review of adequate materials for automotive applications. Composites Part B:

Engineering 2013;44:120–7. doi:10.1016/j.compositesb.2012.07.004.

[3] Gurunathan T, Mohanty S, Nayak SK. A review of the recent developments in biocomposites based on natural fibres and their

application perspectives. Composites Part A: Applied Science and Manufacturing 2015;77:1–25.

doi:10.1016/j.compositesa.2015.06.007.

[4] Jabbar A, Militký J, Wiener J, Kale BM, Ali U, Rwawiire S. Nanocellulose coated woven jute/green epoxy composites:

Characterization of mechanical and dynamic mechanical behavior. Composite Structures 2017;161:340–9.

doi:10.1016/j.compstruct.2016.11.062.

[5] Dittenber DB, Gangarao HVS. Critical review of recent publications on use of natural composites in infrastructure. Composites Part A:

Applied Science and Manufacturing 2012;43:1419–29. doi:10.1016/j.compositesa.2011.11.019.

[6] Joshi S V., Drzal LT, Mohanty AK, Arora S. Are natural fiber composites environmentally superior to glass fiber reinforced

composites? Composites Part A: Applied Science and Manufacturing 2004;35:371–6. doi:10.1016/j.compositesa.2003.09.016.

[7] Saba N, Paridah MT, Jawaid M. Mechanical properties of kenaf fibre reinforced polymer composite: A review. Construction and

Building Materials 2015;76:87–96. doi:10.1016/j.conbuildmat.2014.11.043.

[8] Mustapa IR, Shanks RA, Kong I. Poly(lactic acid)-Hemp-Nanosilica Hybrid Composites: Thermomechanical, Thermal Behavior and

Morphological Properties. International Journal of Advanced Science and Engineering Technology 2013;3:192–9.

[9] Stamboulis A, Baillie CA, Peijs T. Effects of environmental conditions on mechanical and physical properties of flax fibers.

Composites Part A: Applied Science and Manufacturing 2001;32:1105–15. doi:10.1016/S1359-835X(01)00032-X.

[10] Ku H, Wang H, Pattarachaiyakoop N, Trada M. A review on the tensile properties of natural fiber reinforced polymer composites.

Composites Part B: Engineering 2011;42:856–73. doi:10.1016/j.compositesb.2011.01.010.

[11] Yan L, Chouw N, Yuan X. Improving the mechanical properties of natural fibre fabric reinforced epoxy composites by alkali treatment.

Journal of Reinforced Plastics and Composites 2012;31:425–37. doi:10.1177/0731684412439494.

[12] John MJ, Anandjiwala RD. Chemical modification of flax reinforced polypropylene composites. Composites Part A: Applied Science

and Manufacturing 2009;40:442–8. doi:10.1016/j.compositesa.2009.01.007.

18
[13] Asim M, Jawaid M, Abdan K, Ishak MR. Effect of Alkali and Silane Treatments on Mechanical and Fibre-matrix Bond Strength of

Kenaf and Pineapple Leaf Fibres. Journal of Bionic Engineering 2016;13:426–35. doi:10.1016/S1672-6529(16)60315-3.

[14] Liu Q, Hughes M. The fracture behaviour and toughness of woven flax fibre reinforced epoxy composites. Composites Part A: Applied

Science and Manufacturing 2008;39:1644–52. doi:10.1016/j.compositesa.2008.07.008.

[15] Wang H, Xian G, Li H. Composites : Part A Grafting of nano-TiO 2 onto flax fibers and the enhancement of the mechanical properties

of the flax fiber and flax fiber / epoxy composite. COMPOSITES PART A 2015;76:172–80. doi:10.1016/j.compositesa.2015.05.027.

[16] Saba N, Mohammad F, Pervaiz M, Jawaid M, Alothman OY, Sain M. Mechanical, morphological and structural properties of cellulose

nanofibers reinforced epoxy composites. International Journal of Biological Macromolecules 2017;97:190–200.

doi:10.1016/j.ijbiomac.2017.01.029.

[17] Saba N, Paridah MT, Abdan K, Ibrahim NA. Effect of oil palm nano filler on mechanical and morphological properties of kenaf

reinforced epoxy composites. Construction and Building Materials 2016;123:15–26. doi:10.1016/j.conbuildmat.2016.06.131.

[18] Kumar K, Ghosh PK, Kumar A. Improving mechanical and thermal properties of TiO2-epoxy nanocomposite. Composites Part B:

Engineering 2016;97:353–60. doi:10.1016/j.compositesb.2016.04.080.

[19] Al-Turaif HA. Effect of nano TiO2 particle size on mechanical properties of cured epoxy resin. Progress in Or ganic Coatings

2010;69:241–6. doi:10.1016/j.porgcoat.2010.05.011.

[20] Pinto D, Bernardo L, Amaro A, Lopes S. Mechanical properties of epoxy nanocomposites using titanium dioxide as reinforcement - A

review. Construction and Building Materials 2015;95:506–24. doi:10.1016/j.conbuildmat.2015.07.124.

[21] Ravandi M, Teo WS, Tran LQN, Yong MS, Tay TE. Low velocity impact performance of stitched flax/epoxy composite laminates.

Composites Part B: Engineering 2017;117:89–100. doi:10.1016/j.compositesb.2017.02.003.

[22] Oksman K, Skrifvars M, Selin JF. Natural fibres as reinforcement in polylactic acid (PLA) composites. Composites Science and

Technology 2003;63:1317–24. doi:10.1016/S0266-3538(03)00103-9.

[23] Chang LN, Chow WS. Accelerated Weathering on Glass Fiber/Epoxy/Organo-montmorillonite Nanocomposites. Journal of Composite

Materials 2010;44:1421–34. doi:10.1177/0021998309360944.

[24] Soundararajah QY, Karunaratne BSB, Rajapakse RMG. Mechanical Properties of Poly(vinyl alcohol) Montmorillonite

Nanocomposites. Journal of Composite Materials 2010;44:303–11. doi:10.1177/0021998309347040.

[25] Thamaphat K, Limsuwan P, Ngotawornchai B. Phase Characterization of TiO 2 Powder by XRD and TEM 2008;42:357–61.

[26] Nayak RK, Mahato KK, Ray BC. Water absorption behavior, mechanical and thermal properties of nano TiO2 enhanced glass fiber

reinforced polymer composites. Composites Part A: Applied Science and Manufacturing 2016;90:736–47.

doi:10.1016/j.compositesa.2016.09.003.

[27] Zhou Y, Pervin F, Jeelani S, Mallick PK. Improvement in mechanical properties of carbon fabric-epoxy composite using carbon

nanofibers. Journal of Materials Processing Technology 2008;198:445–53. doi:10.1016/j.jmatprotec.2007.07.028.

19
[28] Ahmadi M, Masoomi M, Safi S. Mechanical property characterization of carbon nanofiber/epoxy nanocomposites reinforced by GMA-

grafted UHMWPE fibers. Composites Part B: Engineering 2015;83:43–9. doi:10.1016/j.compositesb.2015.08.006.

[29] Sharma S, Poddar MK, Moholkar VS. Ultrasonics Sonochemistry Enhancement of thermal and mechanical properties of poly ( MMA-

co-BA )/ Cloisite 30B nanocomposites by ultrasound-assisted in-situ emulsion polymerization. Ultrasonics - Sonochemistry

2017;36:212–25. doi:10.1016/j.ultsonch.2016.11.029.

[30] Han X, Zhao Y, Sun JM, Li Y, Zhang JD, Hao Y. Effect of graphene oxide addition on the interlaminar shear property of carbon fiber-

reinforced epoxy composites. Xinxing Tan Cailiao/New Carbon Materials 2017;32:48–55. doi:10.1016/S1872-5805(17)60107-0.

[31] Zhou Y, White E, Hosur M, Jeelani S. Effect of particle size and weight fraction on the flexural strength and failure mode of TiO2

particles reinforced epoxy. Materials Letters 2010;64:806–9. doi:10.1016/j.matlet.2010.01.016.

[32] Goyat MS, Rana S, Halder S, Ghosh PK. Facile fabrication of epoxy-TiO 2 nanocomposites : A critical analysis of TiO 2 impact on

mechanical properties and toughening mechanisms. Ultrasonics - Sonochemistry 2018;40:861–73. doi:10.1016/j.ultsonch.2017.07.040.

[33] Sharma S, Kumar Poddar M, Moholkar VS. Enhancement of thermal and mechanical properties of poly(MMA-co-BA)/Cloisite 30B

nanocomposites by ultrasound-assisted in-situ emulsion polymerization. Ultrasonics Sonochemistry 2017;36:212–25.

doi:10.1016/j.ultsonch.2016.11.029.

[34] Lokasani Bhanuprakash , Abins Ali, Rashad Mokkoth SV. Mode I and Mode II Interlaminar Fracture Behavior of E-Glass Fiber

Reinforced Epoxy Composites Modified with Reduced Exfoliated Graphite Oxide. Polymers and Polymer Composites 2008;16:101 –

13. doi:10.1002/pc.

[35] Veedu VP, Cao A, Li X, Ma K, Soldano C, Kar S, et al. Multifunctional composites using reinforced laminae with carbon-nanotube

forests. Nature Materials 2006;5:457–62. doi:10.1038/nmat1650.

[36] Vijayalakshmi K, Sivaraj D. Synergistic antibacterial activity of barium doped TiO 2 nanoclusters synthesized by microwave

processing. RSC Advances 2016;6:9663–71. doi:10.1039/C5RA28125C.

[37] Lek S, Kongsong P, Sikong L, Niyomwas S, Rachpech V. Photocatalytic Antibacterial Performance of Glass Fibers Thin Film Coated

with N-Doped Photocatalytic Antibacterial Performance of Glass Fibers Thin Film Coated with N-Doped SnO 2 / TiO 2. The Scientific

World Journal 2014. doi:10.1155/2014/869706.

[38] Rwawiire S, Tomkova B, Militky J, Jabbar A, Madhukar B. Development of a biocomposite based on green epoxy polymer and natural

cellulose fabric ( bark cloth ) for automotive instrument panel applications. Composites Part B 2015;81:149–57.

doi:10.1016/j.compositesb.2015.06.021.

[39] Alamri H, Low IM. Mechanical properties and water absorption behaviour of recycled cellulose fibre reinforced epoxy composites.

Polymer Testing 2012;31:620–8. doi:10.1016/j.polymertesting.2012.04.002.

[40] Chatterjee A, Islam MS. Fabrication and characterization of TiO2-epoxy nanocomposite. Materials Science and Engineering A

2008;487:574–85. doi:10.1016/j.msea.2007.11.052.
20
[41] Sun Y, Zhang Z, Moon KS, Wong CP. Glass transition and relaxation behavior of epoxy nanocomposites. Journal of Polymer Science,

Part B: Polymer Physics 2004;42:3849–58. doi:10.1002/polb.20251.

[42] Muñoz E, García-Manrique JA. Water absorption behaviour and its effect on the mechanical properties of flax fibre reinforced

bioepoxy composites. International Journal of Polymer Science 2015;2015:16–8. doi:10.1155/2015/390275.

[43] Alomayri T, Assaedi H, Shaikh FUA, Low IM. Effect of water absorption on the mechanical properties of cotton fabric-reinforced

geopolymer composites. Integrative Medicine Research 2014;2:223–30. doi:10.1016/j.jascer.2014.05.005.

[44] Alamri H, Low IM. Effect of water absorption on the mechanical properties of nano-filler reinforced epoxy nanocomposites. Materials

and Design 2012;42:214–22. doi:10.1016/j.matdes.2012.05.060.

[45] Alamri H, Low IM. Effect of water absorption on the mechanical properties of n-SiC fi lled recycled cellulose fi bre reinforced epoxy

eco-nanocomposites. Polymer Testing 2012;31:810–8. doi:10.1016/j.polymertesting.2012.06.001.

Table 1 Properties of materials [2,29,33]

Properties Flax fibre Epoxy Nano TiO2
Density (g/cc) 1.35 1.15 4
Tensile Strength (MPa) 345 35 51.06

Uniform pressure of 5MPa applied

Release film

4 layers of flax fabric Mould plate (heated at 100°C)

coated with epoxy resin
Fig. 1. Schematic diagram of compression moulding process

21
 300

250 (110)

200

Intensity (a.u)
150 (101) (211)

100
(111)
(200) (220) (310)
50
(002) (301)
0
0 20 40 60 80 100
Degree (2θ)
(a) (b)

Fig. 2. (a) SEM image of nano TiO2 particle (b) X-Ray Diffractions pattern of nano TiO2 particle

(a) Dispersion of nano particles (b) Agglomeration

Fig. 3. SEM image of nano TiO2 particle distribution in epoxy resin for (a) 0.7 (b) 0.9 wt% TiO 2

22
 (a) 90 77.38 78.85
(b) 2.5 2.27
77.25 2.14 2.17
80 71.06 2.06

Tensile Modulus (GPa)

Tensile Strength (MPa)

70 2
60
1.5
50
40
1
30
20 0.5
10
0 0
0 0.5 0.7 0.9 0 0.5 0.7 0.9
TiO2 Content (weight %) TiO2 Content (weight %)

6
(c) 4.8211 4.7161 4.7124
5
4.093
4
% Elongation

0
0 0.5 0.7 0.9
TiO2 Content (weight %)
Fig. 4. Effect of TiO2 content (wt. %) on (a) Tensile Strength (b) Tensile Modulus (c) Percentage elongation (standard deviations are shown as
error bars)

(a) (b)
Poor fibre
matrix
interface

Severe
Adequate fibre
fibre pull
matrix interface
out

23
(c) (d)
Fibre
breakage Presence
of fibre
pull out

Good fibre
matrix
interface

Fig. 5. SEM images indicating fractured surface of flax fibre reinforced epoxy composites with TiO 2 addition by (a) 0% (b) 0.5% (c) 0.7% (d)
0.9% weight percentage

(a) Poor fibre (b)

matrix
interface
bonding

Adequate
fibre matrix
interface
bonding

Good fibre matrix

(c) (d)
interface bonding

Fibre matrix
Fibre pull
debonding
out

Fig. 6. SEM images exhibiting flax fibre and matrix interface of composites with TiO2 addition by (a) 0% (b) 0.5% (c) 0.7% (d) 0.9% weight
percentage

24
 100 88.77 6
(b) 5.03 5.11
80.11 4.81

Flexural Modulus (GPa)

Flexural strength (MPa)

(a) 73.94 76.11 5 4.51

80
4
60
3
40
2
20 1
0 0
0 0.5 0.7 0.9 0 0.5 0.7 0.9
TiO2 Content (weight %) TiO2 Content (weight %)

(c) 3.5
2.94 2.86 2.85 2.83
3
2.5
% Elongation

2
1.5
1
0.5
0
0 0.5 0.7 0.9
TiO2 Content (weight %)

Fig. 7 Effect of TiO2 content (wt. %) on (a) Flexural Strength (b) Flexural Modulus (c) Percentage elongation (standard deviations are shown as
error bars)

25
 9
7.7645 7.8598
8 7.1157 7.2612
7

Impact Strength (kJ/m2)

6
5
4
3
2
1
0
0 0.5 0.7 0.9
TiO2 Content (Weight %)
Fig. 8. Effect of TiO2 content (wt. %) on Impact Strength values (standard deviations are shown as error bars)

20 16.47
Interlaminar shear strength (MPa)

17.12
18 15.61
16 14.41
14
12
10
8
6
4
2
0
0.5 0.7 0.9 0
TiO2 Content (weight %)
Fig. 9. Effect of TiO2 content (wt. %) on Interlaminar shear strength values (standard deviations are shown as error bars)

26
 0% TiO2 0.5% TiO2 0.7% TiO2 0.9% TiO2
120
Finger print region-
100 indicating TiO2 presence

80
3366
Transmittance (%)

2959
60 1602
693
40
547
1502
20

0
3800 3300 2800 2300 1800 1300 800 300
Wavenumber (cm-1)

Fig. 10. FTIR spectra of composites with (0-0.9 wt %) TiO2 addition (For better interpretation refer the web version of this article.)

120
(a)

100

80
Weight Loss %

60

40

20

0
0 100 200 300 400 500 600 700 800
Temperature C°
0% TiO2 0.5% TiO2 0.7% TiO2 0.9% TiO2

27
 (b) Flax composite 0.5% TiO2 0.7% TiO2 0.9% TiO2

1.6
DTG (%/°C)

1.2

0.8

0.4

0
0 100 200 300 400 500 600 700 800
Temperature °C

Fig. 11 (a). TGA (b) DTG curve of composites with (0-0.9 wt %) TiO2 addition (For better interpretation refer the web version of this article.)

0% TiO2 0.5% TiO2 0.7% TiO2 0.9% TiO2

0

-0.1

-0.2
Heat flow (W/g)

-0.3

-0.4
Tg
-0.5

-0.6

-0.7
0 10 20 30 40 50 60 70 80 90 100

Temperature °C

Fig. 12. DSC curve of composites with (0-0.9 wt %) TiO2 addition (For better interpretation refer the web version of this article.)

28
Table.2 Glass transition temperature of composites with TiO2 addition by (a) 0% (b) 0.5% (c) 0.7% (d) 0.9% weight percentage
Sample Glass Transition Temperature (Tg)
0% TiO2 64.13 °C
0.5% TiO2 66.39 °C
0.7% TiO2 69.52 °C
0.9% TiO2 65.66 °C

0% TiO2 0.5% TiO2 0.7% TiO2 0.9% TiO2

1.4
1.2
Wegith Gain(%)

1
0.8
0.6
0.4
0.2
0
0 5 10 15 20 25 30 35
Time (hours)1/2

Fig. 13. Water absorption curves for composite samples with the effect of wt% of TiO 2 (For better interpretations refer the web version
of this article.)

29
 100.00 89.34

Diffusion Coefficient (10-11 m2/sec)

82.02
80.00 75.05

61.05
60.00

40.00

20.00

0.00
0 0.5 0.7 0.9
TiO2 Content (Weight %)
Fig. 14. Diffusion coefficient versus flax fibre reinforced epoxy composite with varying TiO 2 content (wt %) in the matrix.

30