Org. Opto-Elect. 2, No.

1, 37-43 (2016) 37

Organo Opto-Electronics
An International Journal

http://dx.doi.org/10.18576/ooe/020105

© 2012 NSP

Thermoelastic Effect of Vulcanized NBR Loaded by HAF Carbon Black

G. M. Nasr1 and Sh. A. Mansour2,*
1 Physics Department, Faculty of Science, Cairo University, Cairo, Egypt.
2 Basic Engineering Science Department, Faculty of Engineering, Menoufia University, Shebin El-Kom, Egypt.
Received: 21 Feb. 2016, Revised: 22 Mar. 2016, Accepted: 24 Mar. 2016.
Published online: 1 Jul. 2016.

Abstract: The acrylonitrile butadiene rubber (NBR) loaded by various amounts from high abrasion furnace (HAF) carbon black were
fabricated using melt blending technique. The influence of dynamic cyclic elongation on the thermoelastic effect of HAF/NBR samples
has been studied with different stain amplitude reached to 100%. The effect of period of the dynamic cyclic stress on the thermoelastic
behavior of NBR composites was thoroughly studied. All the tested samples exhibited the same thermoelastic behavior. The generated
heat during cycling was promoted the formation of free radicals which are set in random motion. Such motion caused the initial increase
in temperature. On the other hand, the carbon black aggregates are aligned in a direction parallel to the applied stress, giving small rise in
the temperature change of a sample due to the nearing between the particles of filler. The effect of HAF-content (in NBR) on the
thermoelastic behavior was investigated. The change in entropy ∆s and internal energy ∆U with dynamic strain could be calculated as a
function of HAF-black and strain amplitude.
Keywords: Acrylonitrile butadiene rubber (NBR); HAF carbon black; Thermoelastic effect; Dynamic cyclic elongation.

1 Introduction
The usage of conductive elastomers (CEs) has been increased in wide range of application such as switches in
automobile horns, door open sensors and automobile ignition wires. Moreover, CEs have found wide use in
applications based on dissipation of static electricity. Among these, their usage in hospital operating rooms where a
spark could ignite highly explosive anesthetics and truck tires for vehicles carrying explosives. Also, CEs is used in
integrated circuit chips to avoid the damage by static discharge. CE devices are used to electrically connect the chip
leads during shipping and also ground those handling the chips. CEs have been used extensively in electromagnetic
shielding gaskets in military and nonmilitary applications (1). Conductive rubber composites are considered one of the
most types of CEs. Their properties enabled it to use in wide range of applications such as electrostatic charge
dissipation, electromagnetic interference (EMI) shielding, and surface heaters. These materials need the desired
electrical properties as well as sound mechanical properties. Various rubbers are being widely used for preparation of
such composites, e.g., silicone rubber, nitrile, butyl, natural rubber, ethylene—propylene rubber (EPR) and ethylene—
propylene—diene monomer (EPDM) (2,3).
Nitrite rubbers are copolymers based on butadiene and acrylonitrile. The vulcanized nitrite rubber resist a lot of fluids
such as petroleum oils, hydrocarbon fuels, dry-cleaning fluids, fats and vegetable oils. This property can be verified
over the temperature range from - 40 to +135°C and may be reach to 150°C or higher in absence of oxygen. Indeed,
nitrite rubber is used in various applications such as seals, gaskets, diaphragms and hoses for automotive and other
engines, brake linings, oil-well components, belting, shoe soling, printing rolls and adhesives (4-8).
Conducting polymeric composites are traditionally prepared by the blending of conventional polymers with electrically
conductive fillers, and they have important applications in antistatic materials, low-temperature heaters,
electromagnetic radiation shielding, and electric field grading. Among the available fillers, carbon black (CB) has been
extensively employed because of its ability to import high electrical conductivity to an insulating polymer at relatively
low filler content.
The process of deformation of a solid is accompanied by a change in its internal energy and a release or absorption of
heat. If a solid is deformed elastically, this is termed the thermoelastic effect. Its laws have been fairly well studied for

*
Corresponding author e-mail: shehab_mansour@yahoo.com
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 38 G. Nasr, S. Mansour: Thermoelastic Effect of Vulcanized …

many low-molecular weight solids. They have also been studied for polymers (9) where the thermoelastic effect has
specific features caused by a substantial difference in the interactions between atoms that are in one molecule and
atoms belonging to different molecules (10). It was found that a stretched strip of rubber contracts upon heating and that
its temperature rises on sudden stretching. This is contrary to what happens with metals. To explain this behavior many
authors (11,12) had developed quantitative theories based on the idea that network chains undergo configurational
changes by skeletal rotations in response to an applied stress. The important experimental observation reported was that
deformation of rubbers takes place nearly at constant volume. Therefore, changes in entropy must involve changes in
orientation or configuration of the network chains that build the rubber-like materials. The thermoelastic effect
manifests itself in temperature changes, which are associated with structural changes, particularly when these changes
are so rapid that the condition must be considered adiabatic. In such the changes are maximal and occur without
transfer of heat (13). The present work aimed to estimate some of the thermodynamic quantities such as entropy and
internal energy, which are difficult to measure experimentally, via the thermoplastic measurement for acrylonitrile
butadiene rubber (NBR) loaded with different concentration of high abrasion furnace (HAF) black.

2 Experimental Techniques
In fact, the features of the rubber composites are significantly depending on their preparation method such as the order
of adding the ingredients, time of mixing and processing (14). Therefore, all samples have been exposed to the same
circumstances and pass throughout the fabrication procedure. NBR composite samples were fabricated using a two-roll
mill of 300 mm length and 170mm in diameter. The speed of roll was 18 rev /min and gear ratio 1.4 (15). The prepared
compounded rubber was left for 24 hours before vulcanization. The vulcanization process was conducted at 140°C
under a pressure of 40Kg/cm2 for 30 min. For reasonable stability and reproducibility of parameter, samples were
subjected to thermal aging at 343K for 25 days in an electrical oven before measurements (16,17). Table (1) shows the
used amounts of ingredients for each sample. The prepared composites were fabricated from commercial ingredients
according to standard techniques (18).

Table 1 NBR Samples Containing Different loads of Carbon Black

Ingredient
Samples
(phr)*
NBR 100 100 100 100 100 100 100 100 100 100 100
HAF(N- 0 10 20 30 40 50 60 70 80 90 100
330)
Processing 10 10 10 10 10 10 10 10 10 10 10
oil
Stearic
1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
acid
MBTS 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
PBN 1 1 1 1 1 1 1 1 1 1 1
Zinc 5 5 5 5 5 5 5 5 5 5 5
Sulfur 2 2 2 2 2 2 2 2 2 2 2

* Parts per hundred parts of rubber by weight

A homemade cyclic fatigue machine was made and is shown in Figure 1. The rubber specimens used were in the form
of sheets 4 Cm in length 0.5 cm in width and 0.5cm in thickness. For experimental measurements, the specimen was
clamped at both ends in a constant deformation fatigue tester.

Figure 1: Shows the schematic diagram for the homemade constant strain fatigue tester; where (A) Clamps, (B) joint,
(C) Wheel, (D) Counter, (E) Electric motor, (F) Fixed nut, (G) Specimen,(H) movable nut, (I) Electric oven and (J)
Thermocouple

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Org. Opto-Elect. 2, No. 1, 37-43 (2016) / http://www.naturalspublishing.com/Journals.asp 39

All the samples subjected to a given number of strain cycles (250 cycles per minute) with different strain amplitude
(10%, 30%, 50%, 70% and 100%) which could be changed by means of the nut (X). The measurements are not
accumulated i.e., each strain amplitude applied for a new fresh sample for all concentrations. To measure the
temperature, the sample attached to a thermocouple using a Teflon cover (isolated system). The sensitivity of
temperature reading is 0.1°C using a thermometer (PHYWE GTH 1160).

2.1 Theory
Thermoelastic effect refers to change in temperature that occurs for any Hookean solid during is subjecting to
mechanical stress (11). It was predicted by Thomson (19) and measured in iron and rubber by Joule. The explanation of
this effect is very simple and follows directly from the basic concepts of the kinetic theory, namely, that the
deformation of rubbers (at constant temperature) is associated with a reduction of entropy. The first law of
thermodynamics states that the change in internal energy ( dU ) in any process is given by:
dU  dQ  dW  (1)

Where dQ and dW  are respectively the heat absorbed or emitted by the system and the work done on or by an
external force. If there is no internal energy change the heat evolved in an isothermal deformation is:

dQ  dW  at constant T (2)


The work done by a stretching force being necessarily positive implies that the heat absorbed dQ is negative (i.e. that
heat is evolved upon extension). The amount of heat is exactly equal to the work done on the rubber by the applied
force. The physical meaning of this conclusion is as follows; the internal energy of the rubber is purely kinetic and
arises from the thermal agitation of the constituent atoms of the chains. Such energy is consider as a function of
temperature and is independent of the conformations of the chains, i.e., of the state of strain. Since the internal energy
does not change, the work performed by the applied force in an isothermal deformation must be balanced by the
emission of an equivalent amount of heat. If this heat is not emitted but is retained as in an adiabatic extension, the
energy supplied by the applied force is used to increase the molecular agitation, i.e, to produce a rise in temperature.
  dQ 
 
where l is the heat capacity at constant length and  dQ  is the
 C  C
The temperature rise is, therefore,  l

equivalent heat emission in incremental extension dl at constant temperature. Since the process is reversible, we may
put, dQ  Tds and hence:

ds Cl dT
 (3)
dl T dl
Equation (3) gives the entropy change per unit extension in terms of heat capacity which is at the same time equal to
the temperature coefficient of tension at a constant length  f  . For more clear examination of the thermoelastic effect
 
 T  l
phenomenon, it is essential to find a relation between force f, length l and temperature T to the thermodynamic
quantities, entropy s and internal energy u (12, 14, 20). These relation could be summarized in the following (21):

 u   s 
 l   T  l   f
(4)
 T  T
Equation (4) is fundamental importance for rubber elasticity. Moreover, the second law of thermodynamics defines the
entropy change in terms of T and heat absorbed Q by the system in reversible process by the relation:
Tds  dQ (5)
Substituting for dQ by CldT; where Cl is heat capacity; at constant length and dT is the temperature change; then
differentiating with respect to l, equation (5) becomes:
 s  C  T  (6)
l
 l   lT   
 T  

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 40 G. Nasr, S. Mansour: Thermoelastic Effect of Vulcanized …

 s   T 
 
Where 
is the strain. The later equation gives  l 
 
in terms of the easily measurable quantity    through a
thermoelastic experiment.

3 Results and Discussion

Figure 2 represents the temperature change, ∆T, as a function of the duration of the periodic strain (4.2 Hz) at different
strain amplitudes for the investigated NBR composites loaded with HAF concentrations 0phr and 70phr as examples
from all composites.

50
6
(a) (b)
100% 45 100%

5 70%
70% 40
50%
35
4
30

50%

T ( C)
25
T ( C)

o
o

20 30%
30%
2
15

10
1
5
10%
10%
0
0
0 100 200 300 400
0 100 200 300 400
Time (sec) Time (sec)

Figure 2 (a,b): The temperature change ∆T versus the used periodic strain duration (4.2 HZ ) at various strain
amplitudes for 0phr and 70phr composites.
By applying periodic strain; ∆T to stable value depended on the applied strain amplitude. The experimental results
were found to fit an empirical equation of the form:

T  Tm (1  et   ) (7)

Where Tm is the maximum attainable increase in the sample temperature and  is a characteristic time. The value of 
Tm was found to be directly related to applied strain amplitude, for all HAF contents as in Figure 3 for 50phr HAF/NBR
sample, through the relation:
Tm   (8)

Where the proportionality constant  is found to be a function of the carbon content (see Table 2) in the NBR rubber
samples. The fitting parameters Tm ,   and  as a function of HAF contents are given in Table 2.
Equation (7) is purely empirical and may be correlated with thermodynamical variables as follows:
From equation (7) one can write
T 1 Tm

  .   (9)

Where  . is the strain rate.

Using equation (9) in equation (6) yields

 s  Cp  1 T 
   . m
 l   lTo      (10)

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40

35

30

Tm ( C)
25

o
20

15

10
0.2 0.4 0.6 0.8 1.0


Figure 3: The linear relation between maximum temperature change (Tm) and strain amplitude for sample 50phr HAF
content.

Table 2: The values of the fitting parameters T m,   and α as a function of HAF contents.

HAF
contents Strain amplitude (ε) Tm (K)  (sec) α (K)
( in phr )
30% 2.1 230
0 50% 2.9 155 4
30% 3.5 310
10 50% 5.9 205 15.6
70% 9 220
100% 13.6 175
30% 6.5 260
20 50% 7 160 14.2
70% 18 192
100% 14.5 135
30% 7.8 240
30 50% 9.5 170 25.5
70% 22.4 175
100% 23.6 160
30% 9.2 200
40 50% 12.9 165 25.3
70% 24.2 170
100% 25.5 145
30% 13.1 200
50 50% 23 155 34.2
70% 32.5 150
100% 36.9 125
10% 3.5 155
30% 9.5 120
60 50% 29.5 120 42.4
70% 31.4 105
100% 40 105
10% 1.8 175
30% 18.2 155
70 50% 35.2 140 46.7
70% 39.5 115
100% 44 105
10% 8.2 210
80 30% 23.5 170 65.8
50% 34.5 220
10% 7.5 390
90 30% 34 210 132.5

Where Cp is the heat capacity at constant pressure  is the ratio of the specific heats and T0 is the ambient temperature.
Figure 4 illustrates the relation between  s l  and for all the investigated NBR composites. At low carbon HAF
content ( 40 phr) , the vibrating entities appear to be in phase, giving low s l  values. Out of phase motion of
such vibrating entities increase with increasing carbon HAF contents ( 50 phr) . This leads to significantly increase
in the value s l  with increasing  .

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 42 G. Nasr, S. Mansour: Thermoelastic Effect of Vulcanized …

Figure 4: The relation between  s l  and  for NBR loaded samples.

Substituting in equation (4) from equation (10), taking into consideration that the force F in the elastic range can be
replaced by AE , where A is the cross-sectional area and E is the elastic modulus, determined from the initial part of
the stress-strain relation, the equation of internal energy becomes:
 u  EV  C p  Tm  (11)
 l    l   l   .  
   

Where V is the volume of the sample, which is considered as nearly constant. The value of Cp and  used are reported
elsewhere (22). The variation of u l  with strain amplitude  for all samples is given in Figure 5. It is clear that
u l  increases with increasing both strain amplitude and HAF contents. This may be due to the internal friction,
which in turn increases with carbon and strain energy stored in the matrix.

Figure 5: The relation between  u l  and  for NBR loaded samples.

4 Conclusion
All the investigated NBR composites show similar thermoelastic trend. The heat generated during cycling process
results a creation of free radicals with random motion. This motion caused the initial rise in temperature T. The

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Org. Opto-Elect. 2, No. 1, 37-43 (2016) / http://www.naturalspublishing.com/Journals.asp 43

increase in temperature was limited with time due to the probable agglomeration of carbon black fillers which are
aligned in a direction parallel to the applied stress. Thermoelastic experiments dealing with adiabatic heating under
rapid deformation afford a new approach to evaluating important thermal properties of viscoelastic materials. The
thermal effect originates mainly from entropy and internal energy changes occurring during rapid deformation at room
temperature.

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