Author’s Accepted Manuscript

Mechanical behavior and thermal stability of

ultrasonically synthesized halloysite-epoxy
composite

Shakun Srivastava, Anjaney Pandey

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To appear in: Composites Communications
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 Mechanical behavior and thermal stability of ultrasonically synthesized halloysite-

epoxy composite

Shakun Srivastava1,2, Anjaney Pandey1,

1
- Department of Mechanical Engineering, MGCG University, Satna
2
- Department of Mechanical Engineering, PSIT College of Engineering, Kanpur

[email protected]

[email protected]

Abstract

The present investigation deals with a preparation and characterization of composites based on

epoxy reinforced under different loading rates of halloysite nanotubes (HNT’s) according to thermal

stability and their morphological behavior. It has been found that there is appreciable increase in thermal

stability and mechanical properties with the incorporation of HNT’s in epoxy matrix and these properties

have been found maximum at 3 wt.% loading of HNT’s in epoxy matrix. In particular, 30.7% increase in

thermal stability has been achieved and 110.5%, 55.4%, 25.9%, increase in impact strength, ultimate

tensile strength and flexural strength respectively for HNT’s (3 wt.%) epoxy composite. Subsequently,

hardness is also significantly improved on addition of halloysite nanotubes under different loadings.

Strong interfacial adhesion and interaction of halloysite nanotubes with epoxy matrix, influence the

mechanical properties of developed composites.

Microstructural analysis depicted uniform dispersion of HNT’s throughout the entire epoxy matrix

up to 3 wt.% and mechanical properties have been improved due to bridging and cross-linking mechanism

of halloysite nanotube with epoxy matrix. Further considerable decrease in tensile, impact and flexural

1
properties have been found for 4 wt.% and 5 wt.% HNT’s and this may be due to clustering of halloysite

nanotube particles.

Keywords: Epoxy, HNT, SEM, Tensile strength, Thermal properties, Microstructure

1. Introduction

Plastic materials can be classified into two major categories, thermoplastics and thermosets,

according to their responses to temperature. Thermoset polymer possesses three-dimensional cross-linked

structure which never deforms by the application of heat [1]. Thermoset polymers can be obtained by a

large number of crosslinking routes of linear prepolymers or by the formation of cross-linked networks.

Due to the reaction between two monomers, these polymers have superior strength, hardness and thermal

stability when compared to the thermoplastic materials [2]. The properties of thermoset material can be

further increased by reinforcing them with fillers such as clays, carbon nanotube, halloysite nanotube and

graphene nanoplatelets.

Epoxy resin is an important class of thermoset polymer, which is extensively used in polymer

composites because of its excellent chemical resistance, mechanical properties, thermal properties and

low cost [3, 4]. It has been very well documented in the literature for about hundred years that the

incorporation of nanofiller to polymers, polymer glasses and semi-crystalline polymers can be remarkably

improved the performance of polymers [5]. Naturally occurring tubular halloysite clay has attracted great

deal of attention of the researchers because of its multifunctional features. This nanomaterial may have

potential utility as nanofiller in the development of composites for diversified applications in the various

sectors. Halloysite consists of aluminium and silicon in 1:1 ratio for the amount other than clay for

molecular formula of Al2Si2O5(OH)4.nH2O, where ‘n= 2 and 0”, corresponding to hydrated and

dehydrated HNT’s [6]. A relatively low percentage of nanoparticles cause, a major improvement in

mechanical properties [7, 8], thermal stability [9, 10] and adhesion of epoxy resin [11]. Further several
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researchers [12, 13] have investigated the effect of particle volume, shape and size and progressive

researches are underway for proper dispersion of reinforcement. Incorporation of nanofiller into an epoxy

generally provides better results for viscosity built up and shear thinning behavior due to the frictional

interaction [14, 15]. An effective performance of the nanofillers in composites for a variety of

applications strongly depends upon the ability to the dispersion of the nanofiller uniformly over the entire

polymer matrix. Excellent interfacial bonding and interaction between nanofiller and polymers are also an

essential requirement to improve the properties of composites.

The aim of the present work is to develop composites based on epoxy reinforced with halloysite

nanotubes for many applications and to investigate the effect of HNT’s on mechanical and thermal

properties of the epoxy-HNT’s composite with different loading rates. Fabricated composites have been

investigated according to the effect of HNT’s amount on hardness, impact, flexural and tensile properties.

Microstructure confirms the successive addition and distribution of HNT’s and showed the effectiveness

of composite.

2. Materials and methods

2.1 Materials

For fabrication of composites, diglycidyl-ether of bisphenol-A epoxy (DGEBA, LY 556, specific

gravity of 1.16) and triethylenetetramine hardener (TETA, HY 951, specific gravity of 0.95) was used as

a curing agent (supplied by Ciba giegy ltd. Mumbai, India). Epoxy resin and hardener were mixed in a

ratio of 10:1 by weight. The halloysite nanotube (supplied by Sigma Aldrich, USA) used in varying ratios

as a reinforcement to fabricate the composite, the purity of halloysite nanotube is greater than 98 %.

2.2 Fabrication of Composite

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 Halloysite nanotube (1wt.%, 2wt.%, 3wt.%, 4wt.%, and 5wt.%) reinforced epoxy composites were

fabricated by casting method using ultrasonication, whereas the mixture was irradiated for one hour using

a Rivotek sonicator (Model number XT 546, 700 W) at 50% amplitude. It was recorded that the mixture

temperature reaches up to 100℃ during the sonication process. Successively, after addition of a

stoichiometric amount of curing agent (10 wt.% TETA), the mixture was degassed for 30 minutes and

then poured into a stainless steel mould. TETA cured samples in hydraulic compression apparatus has

been fabricated and cured at room temperature (between 35℃ to 45℃) environment for 24 hours.

2.3 Mechanical testing of composites

Tensile properties of developed composites have been determined with the help of a universal testing

machine (Make: Instron model 3382) at room temperature with a gauge length of 50 mm and crosshead

transverse speed of 20 mm/min. Tensile tests were evaluated according to standard ASTM D638 samples.

Further flexural properties were evaluated according to ASTM D790 with a support span 48 mm at room

temperature. Impact properties were evaluated according to ASTM D256 using an impact (Izod) tester

machine (Make: Tenuis Olsem). Durometer was used for hardness testing according to shore D, ASTM

2240 standards at room temperature. For accuracy five samples for each test have been conducted and

shore durometer hardness testing has been carried out for five readings on all specimen surfaces.

2.4 Thermogravimetric Analysis (TGA)

The thermal stability and degradation behaviour of developed composites have been studied with

the help of Perkin-Elmer Pyres TGA (Make: Perkin Elmer). The TGA measurement has been conducted

with a constant heating rate of 10℃/min under a nitrogen atmosphere from 50℃ to 720℃.

2.5 Morphological Study

The surface morphology of the tensile fractured surface has been carried out through a Scanning

electron microscope (Make SEM: JSM-6610, JEOL, NY) with an accelerating voltage of 15 kV. Prior to

4
SEM analysis fractured surfaces of composites have been gold coated with the help of gold sputtering

unit just to avoid the charging effect and to enhance the emission of secondary electrons.

3. Results and Discussion

3.1 Mechanical Properties

Mechanical properties are summarised in Table 1. Accordingly, from Table 1, it is well clear that

properties of the fabricated composites improved by the increase in HNT’s amount addition. From figure

1 (a), it is clear that hardness value is directly proportional to the amount of HNT’s loading rate. This may

be due to the effect of cross-linked density. It is obvious that the impact of cross-linked density on the

epoxy always increases a bonding of reinforcement with the epoxy matrix [1, 2]. In this experimental

study, HNT’s used were small cylinders of average 30 nanometres in diameter with lengths between 0.5

and 10 micrometres, and have excellent level of tendency for the crosslinking. Whereas for other

mechanical properties (tensile, impact and flexural) discussed in this paper, improvement has been

observed up to 3 wt.% HNT’s addition but a considerable decrease in these properties have been found

for 4 wt.% and 5 wt.% HNT’s. This may be due to clustering of HNT particles which confirms that more

amount of HNT, increases hardness value but it affects adversely for other mechanical properties.

Moreover, it is confirmed from Table 1 that there is significant increase in tensile strength, Young's

modulus, impact strength and flexural strength of developed composites. It is also obvious that the

enhancement is more prominent in the case of 3 wt.% loading of HNT’s in the polymer matrix as

compared to the unmodified epoxy polymer.

Transfer of stress from the epoxy matrix to the reinforcement is main responsible factor to

improve mechanical properties of modified composites than the unmodified polymer matrix. In this,

effective stress transfer depends on the interfacial interaction of the polymer matrix with nanofiller and on

the dispersion of the nanofiller particulates in the polymer matrix. It is a well-established fact that the

5
slippage at the filler-polymer interface reduces the stress transfer efficiency due to large strain. Slippage

at the polymer-reinforcement interface is reduced due to the halloysite nanotubes and this might be an

acceptable reason for the improvement of mechanical properties of developed 3 wt.% HNT’s loading

composites [16].

From Table 1, it is evident that there is an increase in impact strength of the composites as

compared to unmodified epoxy and is found to be maximum at 3 wt.% loading of HNT’s. This might be

attributed to the formation of strong and tough materials in the presence of halloysite nanotubes, thus, it

could be said that this increase in impact strength may be due to the intrinsic toughening property of

HNT’s [17]. A better interfacial interaction may also impart an improvement on impact strength with high

absorption energy during deformation. Good dispersion and proper distribution of nanotubes in the

polymer matrix may also offer high impact energy for developed composites (shown in figure 1b). In fact,

the large aspect ratio of halloysite nanotubes may generate complex matrix-interaction during HNT’s

bridging, breaking and pull out that might promote plastic deformation of the matrix [18].

Mechanical properties result also demonstrated that the addition of halloysite nanotubes increases

the modulus of the developed composites. Figure 1 (c and d) depicts that with the addition of HNT’s,

tensile strength has been improved and enhanced upto 55% with respect to unmodified epoxy.This is

thought to be assisted by the rule of mixture theorem [17], which states that the addition of micro and

nanoparticles as reinforcement, impart greater stiffness than the unmodified epoxy matrix [19, 20].

Table 1 demonstrates that the incorporation of 3 wt.% halloysite nanotubes offers an enhancement

in the flexural modulus, whereas, 32% increase in flexural strength as compared to unmodified epoxy

(shown in figure 1e and 1f ). A decrease in the flexural property at higher loading of HNT’s (more than

3wt.%) may be due to the overloading of HNT’s that favours agglomeration of nanotubes.

3.2 Thermal Property

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3.2.1 TGA (Thermogravimetric analyser)

To investigate the influence of HNT’s on the thermal properties of epoxy has been analysed by

TGA and the results are given in Table 2 and figure 2(a-f). All the composites have higher thermal

stability as compared to the unmodified epoxy resin. The onset degradation temperature of unmodified

epoxy has been found to be 101℃ which increases to 132℃ with the incorporation of 3 wt.% halloysite

nanotubes. The incorporation of HNT’s reduces the thermal vibration of C-C bond [21]. Thus, the

hypothesis can be postulated by stating that the composites are in acute need of more thermal energy for

the degradation of the polymer matrix which in turn enhances the thermal stability of the composites.

3.3 Morphology studies by scanning electron microscopy

Fractured surfaces of composites have been studied by SEM are shown in figure 3(a-f). It is

obvious from figure 3(a) that sharp river like fractured patterns have been observed on the epoxy surface,

which ultimately demonstrates the brittle nature of the material. As shown in figure 3(b, c), rough surface

with large cracks can be seen, which confirms a poor resistance to crack initiation and propagation. These

cracks may be caused by the dispersion of HNT’s. From figure 3(b), interfacial precipitation has been

observed (marked by red arrow), which confirms the stress transfer from matrix towards the

reinforcement. Further, this interfacial interaction provides effective distribution of HNT’s on the

locations where small cracks are possible during the shrinkage of epoxy. Generally, the halloysite

nanotube aggregates form defects in the matrix, these defects act as stress concentration centre and

provides localized weakness, therefore lead to large cracks and could be a reason for decrease in the

properties [22, 23]. It is also obvious from the figure 3(d) that uniform surface may be because of

improved dispersion of HNT’s over the epoxy matrix. The uniformly dispersed halloysite nanotubes in

the matrix can form a continuous network, which might support the network of the matrix and release

stress concentration. Besides that, uniformly dispersed halloysite nanotubes might bridge growing cracks,

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thus stabilising and stopping it from developing into larger and harmful crack, thus enhance the various

properties of developed composites [24]. Above 3 wt.% loading of HNT’s, SEM micrographs reveal that

the surfaces of composites have become smoother due to poor dispersion of HNT’s over the epoxy matrix

which might be responsible for decrease in mechanical properties and thermal stability of the composites (

figures 3e, 3f).

4 Conclusions

Halloysite/epoxy composites have been fabricated by casting using ultrasonication and 3 wt.%

loading of HNT’s in epoxy depicted excellent improvement in mechanical and thermal properties as

compared to unmodified polymer matrix. The obtained results from experimental study confirm increase

about 55.4%, 25.9%, 110.9%, 2.8% and 30.7% in tensile strength, flexural strength, impact strength,

hardness and thermal stability respectively for 3 wt.% halloysite nanotubes loading. Whereas, mechanical

and thermal properties (excluding hardness) for composites modified by halloysite nanotubes loading up

to 3 wt.% improved with respect to unmodified epoxy and then decreases for 4 wt.% and 5 wt.% of

HNT’s addition. Moreover, hardness values are directly proportional to the loading rate (wt.%) of HNT’s

in epoxy matrix and increase accordingly. Morphological study reveals that there is uniform dispersion of

HNT’s (3 wt.%) over the entire polymer matrix and because of this reason almost all the mechanical

properties and thermal stability has been enhanced maximum. Thus it can be concluded that halloysite

nanotubes act as an efficient reinforcing agent for the developed composites.

Acknowledgement

We thank Mr Abrar Ahmad and staff members of the department of plastic engineering, Central

Institute of plastic engineering and technology, Lucknow for assistance in fabrication and experimental

works. Authors are also sincerely thankful to Mr Gaurav Maurya, SAI lab, Thapar University, Patiala,

Punjab for assistance in experimental work and SEM facilities.

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Figure 1 (a) Hardness variation w. r. t. HNT/epoxy composite, (b) Impact energy and impact force as a function of
HNT/epoxy composite, (c) Yield’s strength, young’s modulus variation of composite w.r.t. HNT wt. % , (d) Ultimate
tensile stress, young’s modulus variation of composite w.r.t. HNT wt. %, (e) Flexural strength at max load , flexural
modulus variation of composite w.r.t. HNT wt. % , (f) Max flexural load, flexural modulus variation of composite w.r.t.
HNT wt. %

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Figure 2 TGA thermograms for HNT/x/epoxy composites (a) For unmodified epoxy (b) For 1 wt.% HNT’s composite
(c) For 2 wt.% HNT’s composite (d) For 3 wt.% HNT’s composite (e) For 4 wt.% HNT’s composite (f ) For 5 wt.%
HNT’s composite

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15
Figure 3 micrograph for HNT/x/epoxy composites (a) x=0 wt.%, HNT bunch on the fabricated surface (b) x=1 wt.% (c)
x=2 wt.% , interface of the HNT with epoxy (d) x=3 wt.%, uniform distribution of the HNT (e) x=4 wt.%, closer
observation for the HNT grains (f) x=5 wt.%, micro size HNT particles distribution

Table 1: Mechanical properties of composites

Sample Tensile Young’s Elongation Impact Impact Flexural Flexural Shore D

code strength at modulus at break break strength strength modulus hardness
Maximum (MPa) ( %) energy (J/m2) at max (MPa)
Load (MPa) (J) load
(MPa)

X0 48.73 627.14 7.39 0.33 6.4 54.85 1288.11 81.2

X1 55.61 660.87 11.52 0.54 8.3 59.31 1435.32 81.8

X2 61.55 685.01 16.06 0.84 10.4 67.76 1744.36 82.7

X3 75.70 712.76 24.18 1.19 13.5 74.02 1977.70 83.5

X4 67.47 689.71 20.96 1.01 9.9 69.80 1782.57 84.9

X5 61.57 654.11 19.44 0.78 7.7 64.67 1674.86 86.6

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 Table 2: Thermogravimetric analysis

Sample Code X0 X1 X2 X3 X4 X5

Onset Temperature (℃ ) 101 122 125 132 112 131

Final Temperature (℃) 687 720 667 670.7 621 670

Research Highlights

 Halloysite nanotubes were used as reinforcement to fabricate epoxy based composites.

 Composite fabrication was done by casting method using ultrasonication process.
 Tensile, impact, flexural and hardness properties has been investigated.
 Thermal stability of fabricated composite has been analyzed by the Thermogravimetric analyser.
 Micrograph has been investigated of fractured surfaces.

17