International Journal of Materials Science and Applications

2015; 4(2-1): 43-47

Published online January 30 2015 (http://www.sciencepublishinggroup.com/j/ijmsa)
doi: 10.11648/j.ijmsa.s.2015040201.18
ISSN: 2327-2635 (Print); ISSN: 2327-2643 (Online)

Effect of novolac on mechanical and physical properties of

nitrile rubber (NBR)
Mohammed H. Al-Maamori1, Ali Abdul-Amir Al-Zubaidi2, Ahmed Abdulameer Subeh1
1
College of Materials Engineering, Babylon University, Department of Polymer and Petrochemical Industries, Babylon, Iraq
2
College of Engineering / Al-Musayyib, Babylon University, Babylon, Iraq

Email address:
mhalmaamori1959@yahoo.com (M. H. Al-Maamori), axzy128 @yahoo.com (A. A. Al-Zubaidi), ahmedeng6217@yahoo.com (A. A. Subeh)

To cite this article:

Mohammed H. Al-maamori, Ali Abdul-Amir Al-Zubaidi, Ahmed Abdulameer Subeh. Effect of Novolac on Mechanical and Physical
Properties of Nitrile Rubber (NBR). International Journal of Materials Science and Applications. Special Issue: Steel and Direct Reduced
Iron (Sponge Iron) Industry. Vol. 4, No. 2-1, 2015, pp. 43-47. doi: 10.11648/j.ijmsa.s.2015040201.18

Abstract: This research aims to study the effect of addition novolac material (phenol formaldehyde resin, polar) on the
mechanical and physical properties of nitrile rubber (NBR) and the proportion of addition novolac material is(0,10,20,30,40,50
pphr) to a sample of nitrile rubber containing 40 part per hundred rubber (pphr) carbon black as a proportion stationary been
prepared with (factors of vulcanization, accelerators and activators using two-roll mill laboratory, molds, thermal piston and
difference of examination conditions from pressure, temperature and time according to the ASTM), all tests were conducted in
the laboratories of the college of materials engineering - university of babylon and laboratories of babylon tire company. Then
carrying out the process of scheduling the results of laboratory testing and study its diagrams. Where the results showed the
mechanical properties increase in hardness, modulus of elasticity, and resistance to compression, and improved a little in the
tear resistance, especially when the amount of novolac are 10 and 20 pphr, and a decrease in properties (tensile strength,
elongation at break and resilience), also results show increase in adhesion with polyester fibers and nylon fibers when
increasing novolac material. While the results of the physical properties show primitive increase in viscosity, the greatest
torque twisting, scorch time and cure time, then decrease for to increasing novolac material. specific gravity also increases with
increasing novolac material.

Keywords: Nitrile Rubber (NBR), Novolac, Mechanical and Physical Properties

Nitrile Rubber (NBR) is commonly considered the

1. Introduction workhorse of the industrial and automotive rubber products
Rubber has limited applications without reinforcement.so industries. NBR is actually a complex family of unsaturated
that be added polymeric materials including novolac resin to copolymers of acrylonitrile and butadiene. By selecting an
the rubber to reduce the cost and improve the mechanical elastomer with the appropriate acrylonitrile content in
properties, the properties of adhesion and high temperature balance with other properties, the rubber compounder can use
resistance, that meaning the study of mechanical and physical NBR in a wide variety of application areas requiring oil, fuel,
properties of various engineering materials is considered and chemical resistance. In the automotive area, NBR is used
important because of its engineering applications. in fuel and oil handling hose, seals and grommets, and water
The growing use of rubber in engineering applications handling applications [2].
results from its unique properties that include high With a temperature range of –40°C to +125°C, NBR
extensibility, high strength, high-energy absorption, and high materials can withstand all but the most severe automotive
resistance to fatigue. Other attributes are good environmental applications. On the industrial side NBR finds uses in roll
resistance and high resilience. Engineered rubber products covers, hydraulic hoses, conveyor belting, graphic arts, oil
consist of all rubber, or rubber combined with other materials. field packers, and seals for all kinds of plumbing and
Product complexity ranges from that of a simple rubber band appliance applications. Worldwide consumption of NBR is
to complex composites such as radial tires or rubber-metal expected to reach 368,000 metric tons annually by the year
bearings for use in aerospace applications [1]. 2005 [2].
44 Mohammed H. Al-maamori et al.: Effect of Novolac on Mechanical and Physical Properties of Nitrile Rubber (NBR)

NBR is produced in an emulsion polymerization system 1 Passing NBR between the two rolls several times with
[3]. decreasing the distance between the two rolls to the
Novolac is a Phenolic or Phenol formaldehyde (PF) resins extent of (0.5-1) mm .
were the first polymeric resins produced commercially from 2 Addition of sulfur follow by mixing for homogenization
simple low molecular weight compounds [4]. of the materials under room temperature.
Novolacs are formed by the acid catalysed reaction of 3 Add stearic acid, zinc oxide, with the remaining
formaldehyde and phenol in the ratio between 0.5:1 to 0.9:l. quantity from sulfur step (2) together, follow by mixing
The reaction between phenol and formaldehyde in the acidic for homogenization of the materials.
pH range occurs as an electrophilic substitution. The catalysts 4 Add half of the carbon black with operating oil evenly
most frequently used are oxalic acid, hydrochloric acid, across the mill at a uniform rate.
sulphuric acid, p-toluene sulphonic acid (PTSA) or 5 When this portion of the carbon black has been
phosphoric acid. Most commonly, oxalic acid is preferred completely incorporated, open the rolls to 1.65 mm
because colourless resins may be prepared. ln addition, oxalic (0.065 in.).
acid decomposes at high temperatures to CO2, CO and water, 6 Add the remaining carbon black and oil evenly across
and thus oxalic acid will be excluded from recipe. Typically, the rolls at a uniform rate.
1- 6 weight % catalyst is used [5-7]. 7 Addition of accelerator TMTD and MBTS With the
Novolac resins which are thermoplastic in nature must addition of antioxidant TMQ this is followed by mixing
generally be cured by addition of a cross-linking agent. The materials for the purpose of homogenization.
most widely used curing agent is hexamethylenetetramine 8 Set the rolls at 0.8 mm (0.032 in.), follow by mixing for
(HMTA or hexa). Most commonly 8-15 weight% of HMTA homogenization of the materials.
is used [8]. 9 Add materials (such as novolac) with mixing and
Al-Maamory, M.H. 2005[9]. studied the effect of homogenizing.
adding navolacin the range of 0-50 pphr, depending on 10 Add (HMT) after the addition of Novolac.
the mechanical and thermal properties to give the batch 11 Open the mill to give a minimum batch thickness of 6
the ability to absorb shocks and vibrations generated in mm (0.25 in.) and The mixing process continues for
motor vehicles. more time in order to get a good homogenization.
Muhannad K. D. 2007[10]. The researcher studied After preparation of recipes rubber composite by two-roll
reinforcement technique –with copolymer matrix mill laboratory, examination models are prepared to provide
elastomer (Nitrile butadiene rubber), and thermosetting (moldings and condition of examination such as temperature,
resin (novolac) as follows: Addition of novolac resin 0- pressure and time) then a process of vulcanization by the
50 pphr gives a good mechanical and thermal properties thermal piston, according to the ASTM.
which are the principal reason for its uses for the new
composite material (hard material use in cloth drawing Table (1). The composition of the rubber composites
roller). At 30 pphr hardness and tensile strength values Item Recipe Loading level (pphr)
are 75.25 IRHD, 10.787 Mpa respectively. No. Ingredients (1) (2) (3) (4) (5) (6)
The aim of this research to study the effect of adding 1 NBR 100 100 100 100 100 100
2 Activator (zinc oxide) 3 3 3 3 3 3
variable amounts of novolac resin on various properties
Activator (stearic
of nitrile rubber. 3
acid)
1 1 1 1 1 1
4 Carbon black N-326 40 40 40 40 40 40
5 Castor oil 10 10 10 10 10 10
2. Materials and Methods 6 Anti-Oxidant (TMQ) 3 3 3 3 3 3
2.1. Materials Used 7 Accelerator (TMTD) 2 2 2 2 2 2
8 Accelerator (MBTS) 1 1 1 1 1 1
9 Sulfur 1.5 1.5 1.5 1.5 1.5 1.5
Nitrile rubber (NBR), Zinc oxide, Stearic acid,
10 Novolac 0 10 20 30 40 50
Tetramethylthiuramdisulfide(TMTD),Mercaptobenzothiazold 11 HMT 0 1 2 3 4 5
isulfide (MBTS), Hexamethylene Tetramine (HMT), Castor
oil, Sulfur, 2,2,4-trimethy l,1,2-dihydroquinoline (TMQ),
Carbon black (N 326) and novolac used in this study. 3. Characterization and Testing
2.2. Preparation Method 3.1. Mechanical Properties Test

The formulation of the rubber composites are given in 3.1.1. Tensile, Elongation, and Modulus Test
Tables (1) . Tests are carried on samples which are prepared (cutting
Mixing was carried out in a two-roll mills, operations of three dumbbell specimen) from the vulcanized slice .the
kneading and mixing took place on this equipment according cutting take place by hand press.and according to the ASTM
to ASTM D 15. d412-88 by Monsanto T10 tensometer by using special jaws
The ingredients were added according to ASTM D3187-89 for holding tensile test sample which is movable by speed of
as follows: 500 mm /min.
 International Journal of Materials Science and Applications 2015; 4(2-1): 43-47 45

3.1.2. Tear Resistance Test computer with a precision control program .

Examination carried out according to standard ASTM
D624-54, by a device tensile (Tansometer10) and speed (500 4. Results and Discussions
mm/min) after setting the model examination (dumbbell) by
cutting machine models and the work of the incision in the 4.1. Discuss the Results of the Mechanical Properties Test
narrow area of the model by cutting machine (Nicking cutter)
type (Wallace). Then examination by a Tansometer10 to give 4.1.1. Tensile (Mpa), Elongation (%), and modulus (100%
the results (N / mm). Mpa) Tests
Figure 1 shows a decrease in tensile strength when adding
3.1.3. Hardness Test novolac material, because the branching side or the
The test was carried out under ASTM-D2240 Standard entanglements crystalline worked by (the polar phenol) is
using durometer (Hardness shore A). standardized hardness- that reduce the tensile strength of the composite rubber
measuring equipment, a sharp needle was applied directly on product when shed stress in the direction of the longitudinal
to the surface of specimens to measure hardness . data were axis of the chains rubber as a result of the growth of some
averaged over six different positions . micro cracks that cause failure in tensile strength with the
increasing the strength of the rubber compound, as a result of
3.1.4. Specific Gravity Test the increasing proportions load of novolac.
The density tester machine is used . the specification of But in Figure 2, results found that the elongation also
this machine were digital accuracy = 0.0001 g/cm3, type GP- decreases for the same reasons above, with the other reason
120 S, (Matsu Haku, China). first weight the sample is to increase the volumetric fraction of the novolac [10]
(hardness sample) in air then in water at 23°C, by using the within the rubber composition of the synthetic rubber (NBR).
equation (Specific gravity = [sample weight in air/(sample Modulus of elasticity rises with the increasing novolac
weight in air – sample weight in water)] * Specific gravity of material because of the formation of aggregates side and
liquid). increase the number of links interrelation (entanglements), as
3.1.5. Resilience Test in Figure 3.
Resiliency is checked according to specification (ASTM
D1054) using device (Wallace Dunlop Tripsometer) linked to
a digital computer information "Wrpra-wallace Rebound
Resilience Data Computer" records the percentage of
resilient.
3.1.6. Adhesion Test
Tests are carried on prepared samples according to the
ASTM 2229 by tensometer T10 in which we exchange the
special jaws for adhesive test which is movable with speed
of 50 mm /min for measurement the adhesion with wires and Figure 1. Effect of Novolac (pphr) on the tensile strength of NBR matrix
with textile . composite

3.1.7. Compression Set Test

Compression set test (ASTM D395) was performed on
standard test specimen of cylindrical shape of 29 ± 0.5 mm
diameter and 12.5 ± 0.5 mm thickness. Samples were
compressed to 40% of its thickness for 72 hours in
compression set device, then it is left for 30 min before
taking the final thickness of the samples.
3.2. Physical Properties Test Figure 2. Effect of Novolac (pphr) on the elongation of NBR matrix
composite .
3.2.1. Viscosity and Curing Characteristics Test
The test carry on according to ASTM D2084-89 by using
Oscillating dick Rheometer (ODR) for samples prepared
(cutting from recipes rubber composite) in which its control
by upper and lower jaws clutch under 20 Pa and 185 °C for 6
min .
The result draw as a graph of Torque vs. Vulcanized time
as pointed out the following data (maximum torque (1b-in),
minimum torque (1b-in), scorch time (min), cure time
(min) ,viscosity (ML* 2.71) ).The rehometer links to a Figure 3. Effect of Novolac (pphr) on the modulus of NBR matrix composite .
46 Mohammed H. Al-maamori et al.: Effect of Novolac on Mechanical and Physical Properties of Nitrile Rubber (NBR)

4.1.2. Tear Resistance Test (Mpa) voids. i.e rubber recipes at high temperature become stiff thus
Figure 4 shows the effect of adding novolac material on no gaps or cracks inside the recipes rubber, in addition to that
(tear resistance), which is measured in units of Mpa. It is novolac has specific gravity (1.3), higher than that (1.09).
found that recipes rubber increase their tear resistance with
the increasing novolac load until 20 pphr this is because of 4.1.5. Resilience Test
the early starting crosslinking of the chains, but after 20 pphr Addition of novolac to the industrial rubber compound
increased entanglements and decrease in tear resistance. (nitrile rubber) causes a small increase in the resilience up to
the 10 pphr, then followed by a decrease in the resilience due
to increased hardness resulting from the increase in the
density of the branching side, which lead to increased energy
absorbed by the composite rubber, as in figure 7.

Figure 4. Effect of Novolac (pphr) on the Tear resistance of NBR matrix

composite

4.1.3. Hardness Test (ShA) Figure 7. Effect of Novolac (pphr) on the Resilience of NBR matrix
Figure 5 shows the relationship between the hardness and composite .
the addition weights of novolac to the recipe rubber
composite, results showed that increasing the proportion of 4.1.6. Adhesion Test
novolac which leads to increased hardness. The increase in Figure 8 shows the increase in the strength of adhesion
hardness is attributable to strong tangles between the rubber with the increasing novolac addition, the reason is to increase
and the novolac which produces an increase in surface the density of interrelation of compound rubber, which leads
tension. It means that the surface of the product becomes to increased adhesion with fibers (polyester and nylon), as
resistant to penetration [9]. the proportion reach 20 and 30 pphr the adhesion of novolac
with polyester fibers higher than with nylon fibers, when the
proportion exceed 50 pphr the adhesion decreases for both
fibers.

Figure 5. Effect of Novolac (pphr) on the hardness of NBR matrix composite

4.1.4. Specific Gravity Test

Figure 8. Effect of Novolac (pphr) on the Adhesion of NBR matrix
composite .

4.1.7. Compression Set Test (%)

Figure 6. Effect of Novolac (pphr) on the Specific gravity of NBR matrix

composite

Figure 6 shows the relationship between specific gravity

and proportions of novolac added to recipe rubber composite, Figure 9. Effect of Novolac (pphr) on the Compression set of NBR matrix
it is noted an increase in specific gravity with the increase in composite
the proportion of the novolac, and this behavior is attributed
to the lack of spaces between the rubber chains because Results showed that the compressive strength increases
novolac enters between the rubber chains and thereby dictate with the proportion of the novolac ,this is because the
 International Journal of Materials Science and Applications 2015; 4(2-1): 43-47 47

increase in the density of entanglements and a decrease in the the amount of materials solidified (HMT) that are initially
movement of rubber chains and increase the rigidity or good down to the 10 pphr of the novolac after this they
stiffness compound rubber, and these entanglements reduce become few and they are inadequate to strengthen (hardness)
susceptibility retrieval of compound rubber, and this result each quantity of the novolac, and therefore rubber need more
agree with the results of two former researches [11] as in time to complete the process of vulcanization.
Figure 9.
4.2. Discuss the Results of the Physical Properties Test 5. Conclusions
4.2.1. Viscosity (Mooney) & Max. Torque (MH lb*inch). 1 New polymer composites were prepared from the
Figure 10 shows the relationship between viscosity and the mixing novolac with (NBR).
proportion of the novolac added to recipe rubber composite, 2 Tensile strength decrease (from 13.579 Mpa to 8.085
noticed an increase of viscosity with the increasing the Mpa) with increasing the novolac content .
novolac because it has the characteristics of elastomeric 3 Elongation at break decrease (from 767 % to 193.5 % )
material at a temperature of 185°C but after reaching 20 pphr with increasing the novolac content .
novolac or above, the viscosity and fluctuating becomes low 4 modulus of elastcity increase (from 1.66 Mpa to 5.716
because of the reverse effect to increase the hardness and Mpa ) with increasing the novolac content .
density of entanglements. At the same shape note a rise in the 5 Hardness increase (from 57.2 to 85.166 ShA ) with
values of the greatest torque twisting, Any more pressure increasing the novolac content .
needs to purpose of recipe flow inside the mold as a result of 6 Other properties such as tear resistance, compression
entanglement, which do the novolac with rubber chains, but set and specific gravity increase, but resilince decrease
after reaching a 30 pphr novolac fluctuating in the torque with increasing the novolac content .
values for the same reasons above. 7 Physical properties such as viscosity, max.Torque,
scorch time, cure time, their values varies with
increasing the novolac content .
8 Best adhesion with the fiber at 40 pphr novolac.

References
[1] J. G. Sommer, Rubber World, December, 1996, p. 18.
[2] Table 2, Worldwide Long Term New Rubber Consumption
Figure 10. Effect of Novolac (pphr) on the (Viscosity, Max. Torque) of NBR Forecast by Elastomer Type, IISRP Worldwide Rubber
composite. Statistics (2001).

4.2.2. Scorch Time (TS5 Min) & Cure Time (TC90 Min) [3] Table 14, Nitrile Dry Rubber (NBR), IISRP Synthetic Rubber
Manual,13th Edition, (1995).
[4] A.Knop and W.Scheib, Chemistry and Application of Phenolic
Resins, Springer-Verlag,Berlin Heidelberg, New York (1979).

[5] N.Kornblum, R.A.Smiley, R.K.Blackwood and D.C.lffland, J.

Amer. Chem.S0c. 77, 7269 (1955).
[6] Humayun Manda] and Allan S. Hay, Polymer, 38 ,26, 6267-
627l(1997).
[7] Martin R.W. The Chemz'stry of Phenolic Resz'n.s', New York,
J .Wei1y, (1956).
Figure 11. Effect of Novolac (pphr) on the (Scorch Time, Cure Time) of NBR
composite. [8] Kopf P.W., Wagner,E.R., Polym.Sci. Poly. Chem. Ed.,1l, 939
(1973).
Figure 11 shows the relationship between scorch time and
the ratio of the novolac. The increase in the proportion of the [9] Al-Maamory, M.H " Mechanical & Physical Properties of
Rubber Composite For Engine Mounting " Ph. D. thesis,
novolac leads to a small increase in the Scorch time and then
University of Technology , Baghdad, 2005.
decreases in the value, this is attributed to the entry of the
novolac with chains during a rubber vulcanization process, [10] Muhannad Kh. D. " Design and Industrialization Recipes of
which link rubber chains, thereby reducing the Scorch time. Cloth Drawing Rollers From Rubber composite material " M.
D. thesis, University of Babylon, 2007.
The same figure shows the relationship between the time of
vulcanization (cure time) and the ratio of the novolac, It is [11] Schuur MVD, Gaymans RJ. Influence of chemical crosslinks
noted that increase in the proportion of the novolac leads to on the elastic behavior of segmented block copolymers.
the increasing time of vulcanization and the reason for this is Polymer 2005;46:6862–8.