DOI 10.

1515/secm-2013-0292Sci Eng Compos Mater 2014; aop

Mayank Agarwal, Mohamand Arif, Ankita Bisht, Vinay K. Singh* and Sunanda Biswas

Investigation of toughening behavior of epoxy

resin by reinforcement of depolymerized latex
rubber
Abstract: An epoxy resin (EP) matrix has been modified with depolymerized natural rubber (DNR). The 0.5,
1.0, 1.5, 2.0, and 2.5 wt% DNR-filled epoxy were used
for the present investigation. The primary aim of this
development is to scrutinize the mechanical properties
of such cured epoxy filled with DNR. When the rubber content was low, the mechanical strength was low
and the free volume of DNR in epoxy matrix was less.
With the increase in rubber content, the free volume of
rubber in the composite increases and the mechanical
strength increases; however, after a specific weight percentage of rubber, if we increase the amount of rubber,
the mechanical strength decreases and the free volume
of rubber in the composite increases quickly, but with
the increase in DNR weight percentage in epoxy matrix,
the hardness decreases. The scanning electron microscopy (SEM) results justified the results obtained from
the mechanical tests.
Keywords: depolymerized natural rubber; epoxy resin;
mechanical properties.

*Corresponding author: Vinay K. Singh, College of Technology, G.B.

Pant University of Agriculture and Technology, Pantnagar-263 145,
Uttarakhand, India, e-mail: vks2319@yahoo.co.in
Mayank Agarwal, Mohamand Arif, Ankita Bisht and Sunanda
Biswas: College of Technology, G.B. Pant University of Agriculture
and Technology, Pantnagar-263 145, Uttarakhand, India

composite materials. However, general epoxy systems

usually suffer the shortage of toughness due to the high
levels of cross-linking, which can and usually does result
in brittle behavior. Liquid rubber can be used as a toughing material for EP because it is normally derived from
synthetic rubber. During the polymerization, the rubber
phase separates because it becomes less miscible with
the epoxy matrix, forming a sludge of rubber that is dispersed in the EP matrix. Several methods have been proposed to increase the toughness of EP by the addition of
rubber in uncured EP and then controlling the polymerization reactions in order to restrict the phase separation
[16]. The rubbery materials that are added to the uncured
epoxy are types of copolymers with variable acrylonitrile
contents. The studies reported that, to modify EP, mostly
modified liquid rubber was used, such as liquid rubber
modified by divinylbenzene (DVB), hydroxyl terminated
butadiene (HTPB), carboxyl terminated butadiene-acrylonitrile (CTBN), or isocyanate terminated polybutadiene (NCOPBER) [4, 79]. However, due to the increasing
awareness of environmental issues, natural latex rubber
has attracted great interest because it is a renewable
resource. In the present study, natural rubber latex is used
as a toughing material for EP. The properties of modified
epoxy are studied by tensile test. The dispersion of rubber
in the matrix of epoxy is verified by the scanning electron
microscopy (SEM) test.

2 Materials and methods

1 Introduction
2.1 Epoxy resin
Epoxy resins (EP) are used in a variety of applications
because they are a very important class of thermosetting polymers that exhibit high tensile strength, excellent chemical and corrosion resistance, good thermal
stability, low density and low creep, and reasonable
performance at elevated temperature. Hence, they are
widely used in structural adhesives, surface coatings, and
electrical laminates and as matrix resins for reinforced

The bisphenol A-type EP (CY230) used for this study

was purchased from M/s Petro Araldite Pvt. Ltd.
(Chennai, India). Epoxy (CY230) is widely used in industrial application because of its high strength and good
mechanical adhesiveness. It is also a good solvent and
has good chemical resistance over a wide range of
temperature.

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2M. Agarwal etal.: Investigation of toughening behavior of epoxy resin

2.2 Hardener HY951

The hardener HY951 purchased from M/s Petro Araldite Pvt.
Ltd. was used as a curing agent. In the present investigation,
9 wt% has been used in all materials developed. The weight
percentage of hardener used in the present investigation is
as per the recommendation of Singh and Gope [10]

2.3 Natural rubber latex

Natural rubber latex (NR) was purchased from M/s Allied
Business (Pantnagar, India). It has 60% dry rubber content.
The NR has outstanding flexibility and high mechanical
strength. Moreover, it is a renewable resource, whereas its
synthetic counterparts are mostly manufactured from nonrenewable oil-based resources. Therefore, NR has created
a high level of interest regarding its use and its derivatives.

2.4 Preparation of the material

2.4.1 Depolymerization of NR
Depolymerization means opening the active linkage in the
polymer backbone by the reaction of a reagent with reactive
polar group. Depolymerization can reduce the chain length
of natural rubber. In general, a depolymerized natural
rubber (DNR) can be obtained by mastication, photolysis,
chemical decomposition, or the like of the natural rubber.
Mastication is a method for accelerating reduction in the
molecular weight by breaking the rubber molecular chains
of the raw rubber through a mechanical action and heating
in a roller mill or internal mixer and then adding a peptizing agent such as a mercaptan [11]. Vitaly and Eduardo [12]
used the photolysis method for breaking the molecular
chains with light energy, that is, ultraviolet light. Another
approach that has been used to reduce the molecular
weight of natural rubber is chemical decomposition. This
method is the degradation of molecular chains by chemical
reagents. In 1996, Tanaka etal. [13] proposed the process for
depolymerizing natural rubber, which comprised adding
a carbonyl compound to natural rubber latex or deproteinized natural rubber and then subjecting the resulting
natural rubber or deproteinized natural rubber to air oxidation in the presence of a radical-forming agent. The results
showed that the DNR having a narrow molecular weight
distribution can be obtained at high reaction efficiency.
In the present method, 60% total dry content natural
rubber latex was diluted by distilled water to a concentration of 5 wt% based on rubber content followed by the

addition of CH3CH2COCH3 and K2S2O8 in an amount of 46

vol% of total volume and 2 wt% based on the rubber content,
respectively. The pH of latex was adjusted to about 910 with
10 wt% aqueous KOH solution. Then, the reaction mixture
was mechanically stirred at a speed of 200300rpm at 60C
on the sand (for the equal distribution of heat) for 24h in
the presence of air. At the end of the reaction, the reaction
mixture was coagulated by 1 wt% aqueous CaCl2 solution.
The coagulated substance was dissolved in n-hexane and
stirred with magnetic bar for 12 h. Then, the resulting solution was allowed to stand overnight and filtered. The filtrate
mixture was bathed with methanol followed by vacuum
drying at 40C until the weight is made constant.

2.4.2 Preparation of rubber-filled EP

The DNR was dissolved completely in EP (CY230) at 100C
using a mechanical stirrer at a speed of 500rpm for 2 h. After
2 h, the whole solution is taken out and allowed to cool to a
temperature of 80C. When a temperature of 80C has been
attained, a 9 wt% hardener is mixed immediately. After the
addition of the hardener, viscous solution was again mixed
mechanically by a high-speed mechanical stirrer. The
viscous solution so obtained is poured into different moulds
for sample preparation for tensile testing. The compositions
of cured epoxy filled with DNR are given in Table 1.

3 Results
3.1 Characterization of cured epoxy filled
with DNR
The specimens were gold coated and examined by SEM
using a LEO435V6 instrument. The accelerating voltage
was kept at 10 kV and magnification factor of 250. The
SEM test was conducted on the fractured surface to see the
mechanism of the fracture. The state of dispersion of DNR
Table 1Compositions of cured epoxy filled with DNR.
Designation of
composition
C0
C1
C2
C3
C4
C5

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EP (CY230)
(wt%)

Hardener (HY951)
(wt%)

DNR
(wt%)

100
100
100
100
100
100

9
9
9
9
9
9

0.0
0.5
1.0
1.5
2.0
2.5

M. Agarwal etal.: Investigation of toughening behavior of epoxy resin3

into the resin matrix plays a significant role on the improvement of the mechanical properties of the cured epoxy. It is
seen from Figure 1AD that DNR are well dispersed in the EP
matrix and sharp surface failure occurs in all the tests. The
absence of any voids indicates a good adhesion between
the DNR and epoxy matrix. Figure 1AC shows that the DNR
added to the epoxy matrix has completely bonded with it
and there is no free volume of DNR in the epoxy matrix.
From Figure 1D, it is evident that there is some free volume
of DNR that has not chemically bonded with the matrix, as
estimated from the observations. Due to this reason, the
mechanical strength increases up to 1 wt% rubber and then
decreases with further increase in the weight percentage of
rubber due to the excess or free volume of rubber.

3.2 Mechanical properties

The tensile test specimen (Figure 2) prepared for each
weight percentage of DNR was loaded in uniaxial tension
on a 100 kN servohydraulic universal testing machine
(ADMET, Norwood, MA, USA) at 0.1mm/s crosshead speed
according to ISO 1608:1972. The standard gauge length of

the specimen should be given by L0 = 5.65A0, where A0

is the cross-sectional area of specimen (m2) and L0 is the
standard gauge length of the specimen (m).
From the stress strain curves as shown in Figure 3,
the ultimate strength, modulus of elasticity, and percent
elongations were determined. The room temperature and
humidity during testing were 32C and 88%, respectively.
Remarkable differences have been observed in the stress
strain behavior due to the addition of DNR in the EP matrix.

3.3 Tensile properties

From the results, remarkable differences can be seen on
the ultimate tensile strength of DNR-filled cured epoxy
having different weight percentages of DNR tested at
0.1mm/s crosshead speeds given in Table 2. It can be seen
from the results that, for all specimens containing 1.0 wt%
DNR, the ultimate tensile strength is highest from among
the other compositions reported. About 42% increase in
ultimate tensile strength due to the addition of 1.0 wt%
DNR has been noticed compared to pure epoxy. This
increase in strength is observed due to the intermolecular

Figure 1SEM images of fracture surface for several cured epoxy: (A) pure epoxy, (B) 0.5 wt% rubber, (C) 1.0 wt% rubber, (D) 1.5 wt% rubber.

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4M. Agarwal etal.: Investigation of toughening behavior of epoxy resin

Gage
length

Grip section

14

80

13

Dia. or width
Reduced section

Figure 2Specimen of tension test.

12
11

60

10
50

9
8

40

30

80
70

Ultimate strength (MPa)

% Elongation

20
0

60

Elongation (%)

Width of
grip section

Ultimate strength (MPa)

70

0.5

1.0

1.5

4
2.5

2.0

Stress (MPa)

Rubber (wt%)
50
40
0 wt% of R
0.5 wt% of R
1.0 wt% of R
1.5 wt% of R
2.0 wt% of R
2.5 wt% of R

30
20
10
0
0

0.02

0.04

0.06

0.08

0.10

0.12

0.14

Strain

Figure 3Stress strain curve of different weight percentages of DNR.

bonding between the rubber particle to the resin particles.

A further addition of DNR on the EP decreases the ultimate tensile strength of the DNR-filled cured epoxy due
to excess rubber particles, which is present free without
bonding. Similar observations have been noticed for
percent elongation as shown in Figure4. About 2.47 times
increase in the modulus of elasticity has been observed
due to the addition of 1.0 wt% DNR at 0.1mm/s crosshead
speed. A further addition of the DNR decreases the percent
elongation but is higher than the neat epoxy material.
About 1.4 times increase in the modulus of elasticity is
noticed for the 2.0 wt% DNR-filled cured epoxy.
The variation of the modulus of elasticity and toughness with the variation of rubber weight percentage is

Figure 4Mechanical properties of cured epoxy filled with different

weight percentages of DNR.

as shown in Figure 5. In Figure 5, it is seen that a nonlinear relation exists between the modulus of elasticity
and weight percentage of filler materials. The maximum
modulus of elasticity is found for neat resin. It has been
noticed that toughness is found to be maximum at the
addition of 1.0 wt% DNR compared to pure epoxy. This
increase in strength is due to the proper intermolecular
bonding between rubber particle to the resin particles. A
further addition of DNR on the EP decreases the toughness of the DNR-filled cured epoxy due to excess rubber
particles, which is present unbonded. Keeping in view the
importance of the modulus of elasticity and toughness in
design and analysis, an attempt has been made to model
an empirical relation of the following type to interpret the
filler polymer interaction.
Up to 1.0 wt% DNR
E/T=1101 (WR ) 2 -2014 (WR )+1087, R 2 =1

(1)

More than 1.0 wt% DNR

E/T=-195.1 (WR ) 2 +972.5 (WR )-792.4, R 2 =1

(2)

Table 2Tensile properties of cured epoxy filled with different weight percentages of DNR.
Designation of
composition
C0
C1
C2
C3
C4
C5

DNR (wt%)

Ultimate
strength (MPa)

Elongation (%)

Toughness
(MPa)

Modulus of
elasticity (MPa)

0.0
0.5
1.0
1.5
2.0
2.5

47.40
52.28
67.33
41.30
39.89
35.26

5.10
9.50
12.58
11.00
7.17
6.80

1.737
3.001
5.229
2.956
1.416
1.226

1889.28
1067.73
912.74
671.76
526.75
513.89

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M. Agarwal etal.: Investigation of toughening behavior of epoxy resin5

45

2000
Modulus of elasticity
Toughness

44
5

1400

1200
1000

Hardness (HRR)

43

1600
Toughness (MPa)

Modulus of elasticity (MPa)

1800

42
41
40
39
38
37

800

36

600

35

400
0

0.5

1.0

1.5

2.0

0
2.5

0.5

1.0

1.5

2.0

2.5

Rubber (wt%)

Rubber (wt%)

where E and T are the modulus of elasticity in MPa and

toughness in MPa, respectively. WR denotes the weight
percentage of DNR. In the present case, toughness behavior is the opposite after the addition of more than 1 wt%
DNR.

3.4 Hardness
All hardness tests are conducted on a Rockwell hardness
testing machine supplied by P.S.I. Pvt. Ltd. (New Delhi,
India) on R scale. The effect of the weight percentage of
DNR on the hardness values of DNR-filled cured epoxy is
shown in Figure 6. It is found that the hardness of neat EP
is 44 HRR. The hardnesses of the fabricated cured epoxy
filled with 0.5, 1.0, 1.5, 2.0, and 2.5 wt% DNR are 43, 41, 39,
37, and 36 HRR, respectively, as given in Table 3.
Figure 6 indicates that the hardness decreases with
the DNR content, reflecting the reinforcement formed in
the DNR-filled cured epoxy. The variation of the ratio of
the modulus of elasticity with the hardness of DNR-filled
cured epoxy is shown in Figure 7. Figure 7 illustrates that
the hardness value follows a nonlinear relation with the
modulus of elasticity of the DNR-filled cured epoxy. An
attempt has been made to correlate the modulus of elasticity with hardness. The following correlation has been
obtained:

Figure 6Hardness of cured epoxy filled with different weight

percentages of DNR.

Table 3Hardness of cured epoxy filled with different weight

percentages of DNR.
Designation of
composition
C0
C1
C2
C3
C4
C5

DNR (wt%)

Hardness

0.0
0.5
1.0
1.5
2.0
2.5

44
43
41
39
37
36

50
Modulus of elasticity (MPa)/hardness (HRR)

Figure 5Modulus of elasticity and toughness of cured epoxy filled

with different weight percentages of DNR.

45
40
35
30
25
20
15
10

E/H
Poly. (E/H)

5
0
0

0.5

1.0

1.5

2.0

2.5

Rubber (wt%)

Figure 7E/H ratio of cured epoxy filled with different weight

percentages of DNR.

E/H=-6.950 (WR ) 5 +49.76 (WR ) 4 -129.8 (WR ) 3

+151.8 (WR ) 2 -85.44 (WR )+42.93, R 2 =1,

(3)

where E and H are the modulus of elasticity in MPa and

hardness in R-scale, respectively. WR denotes the weight

percentage of DNR. Equation (3) indicates that the nonlinear relationship between the modulus of elasticity
and hardness has a good correlation. It shows that the

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6M. Agarwal etal.: Investigation of toughening behavior of epoxy resin

modulus of elasticity is directly related to the hardness of

this type of cured epoxy filled with DNR.

EP. Regression models were developed to simulate the

mechanical behavior of such materials from the volume
content of the DNR.

4 Conclusions

Acknowledgment: The authors express their gratitude

and sincere thanks to Department of Science & Technology, India for providing finance to carry out this research
work smoothly.

A DNR-filled cured epoxy was prepared. Such DNR-filled

cured epoxy was experimentally characterized by means
of microscopy, tensile testing, and hardness testing.
Remarkable improvements in the mechanical properties have been noticed due to the addition of DNR in

Received November 17, 2013; accepted December 14, 2013

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