Chapter 2

ater rials and Experimental ~ e t h o d s

Abstract
The properties of the materials used for the study are discussed in this
chapter. The experimental techniques used for compounding, curing and the
measurement of physical, transport and mechanical properties are discussed.

The procedures for the analysis of the various parameters and properties are
given in this chapter.

65 Materials and Experimen~alMefhods

Materials Used
Nitrile rubber (NBR) (Aparene N553NS) used for the study was obtained

from Gujarat Apar Polymers Ltd., Mumbai, India. The rubber from the same lot

has been used throughout the experiment.

Natural rubber (NR) was obtained from Rubber Research Institute of
India, Kottayarn, India. This rubber satisfied the Bureau of Indian Standard's

specification for ISNR-5 grade natural rubber.

Epoxyprene used is cis- 1, 4-polyisoprene with epoxide groups randomly

dispersed along the polymer backbone. Epoxyprene-50 (ENR-50) with 50 mol%

epoxidation was obtained from Rubber Research Institute of Malaysia, Malaysia.

The specification parameters for NBR, ISNR-5 and ENR-50 are given in Table 2.1.

Table 2,l Specifications of NBR, ISNR-5 and ENR-50

Materials
Characteristics
Volatile matter (%)
- .
Antioxidant (%)
Organic acid (%)
Nitrile rubberSoap (YO)
(Aparene
Mooney viscosity
N553 NS)
(ML1+4 1 OOC)
Bound acrylonitrile (%)
Intrinsic viscosity (dllg)
Epoxidised
Epoxidation level (mol%)
natural rubber- Glass transition temperature ("C)
(Epoxyprene) Density (kg/m3)
Solubility parameter (Jm-3)-IR
Number average mol. wt (M,)
Gel content (%)

Natural rubber
(ISNR-5)

Glass transition temperature (OC)

Density (kg/m3)
Solubility parameter (Jm-3)1/2
Number average moi. wt (M,,)

0.130
1.400

Materials and Experimental Methods 66

2.1.1.

Rubber chemicals

Elemental sulphur and dicurnyl peroxide used as vulcanising agents in this

study were chemically pure grades. The accelerators used in this study were

commercial grade Dibenzothiazole disulphide (MBTS), tetra methyl thiuram

disulphide (TMTD) and Ncyclohexy1-2-bemthiamle sulphenamide (CBS). Zinc

oxide, sodium carbonate, trimethyl dihydro quinoline (TDQ), stearic acid and

pre-vulcanisation inhibitor, N-(cyclohexylthio)phthalimide

used were also

cheniically pure grades.

2.1.2.

Fillers

Four types of carbon black were used as fillers in this work. They were
super abrasion furnace (SAF), intermediate super abrasion furnace (ISM), high
abrasion furnace (HAF) and semireinforcing furnace (SRF). The characteristic
features of these fillers are given in Table 2.2. Another filler used in this work is

silica (Ultrasil VN3).

Table 2.2 Characteristics of black fillers
Type

Grade

Iodine adsorption*
(mglg)

Pour
density(g/I)

Particle
size(nrn)

SAF

NIlo

145

335

20

ISAF

N220

121

345

23

HAF

N330

82

375

29

SRF

N770

31

379

60

*Accordingto IS- 1304

67 Ma1eriaIs and Experimental Methods

2.1.3. Solvents

The solvents used in this work were benzene, toluene, p-xylene and
dichloromethane of LR grade manufactured by E-Merck (India) Ltd., Mumbai,
India.. Their measured physical properties agree well with the literature values'.

Relevant data are given in Table 2.3.

Table 2.3 Physical properties of solvents

Boiling point Melting point

w>

Solvent

Refractive

("c)

Density at
2 5 'C (O/cc)

index at 25 O C

Benzene

80.10

5150

0.874

1.4979

Toluene

1 10.62

-95.0

0.867

1.494 1

pxylene

138.35

-25.0

0.860

1.4934

Dichlommethme

40.50

-96.70

1.325

1-4246

2.1.4.

Plasticizers
The plasticizers used in this study were commercial g a l e dibutyl

phthalate, dioctyl phthalate, dioctyl adipate and dioctyl sebacate The

characteristics of these plasticizers are shown in Table 2.4.
Table 2.4. Physical properties of plasticizers

Plasticizer

Molecular
weight

20C (rnPa.s)

Specific
gravity

Boiling
point CC)

DBP

278

19-20

1.05

339

DOA

370

14- 15

0.93

DOP

390

40-45

0.99

370

DOS

426

21

1.5

249

Viscosity at

--

. .-,

Malerials and Experimental Methods 68

2.2. Preparation of Rubber Compounds

The basic formuIations used throughout this work are given in Table 2.5.
The effect of vulcanising system on properties was studied by selecting

conventional, efficient, peroxide and mixed vulcanising systerns. Mixes A, B, C

and D represent the conventional, efficient, mixed and peroxide vulcanising systems
respectively. It may be noted that both conventional and efficient systems are based on
accelerated sulphur formulations but the sdphur/accelerator ratio is higher for the

former. The mixed system contains both sulphur and dicumyl peroxide

as

vulcanising agents. Nitrile rubbednatural rubber blend membranes were prepared

by the masterbatch technique. The mix A is used to make NBR masterbatch. The

NR formulation used is given in E, The formulations used to make NR and NBR

masterbatches for the transport of milk and ghee through NBWNR blends are
given in F (NR)and G (NBR). Here the plasticizers used are DBP and DOA.In
order to study the effect of fillers, NBR membranes were conventionally
vulcanised (H) with four types of carbon blacks viz., SAF, ISAF, HAF and SRF
under different degree of loading. The blends of NBR with ENR were prepared
by the same technique used for NBWNR blends. The ENR formulation used is

given in I.

69 Materials and Experimental Methods

Table 2.5. Formulation of the mixes (phr)

Ingredients
NBR

A
100

NazC03

5.0
1.0

TMTD
MBTS
DCP (40 Yo)
Sulphur
TDQ
PVI
Plasticizer
Carbon black
Silica

100

100

100

100

5.0
1.0

5.0
1.0

1.0

CBS

NR
ENR
Zinc oxide
Stearic acid

1.5
1.5

1.5

0.5

1.0

4,O
1.5

100

100

100

100

5.0

5.0

5.0

5.0

5.0

1.5

3.0

3.0

1.0

2.0

0.6

0.9
0.1

0.3
1.7
0.18

1.6
2.4

4.0

1.0

2.5
1.0

1.0
1.0

1.86
1.0

25
50

35

1.5

0.3
2.0

0.2

40

* 10,20,30 and 40 phr

2.2.1. Compounding of mixes

The different rubber chemicals were incorporated into the rubber matrix
using a two roll mixing mill (150 x 300 mm) at a nip gap of 1.3 mrn and at a

friction ratio 1: 1.4 as per ASTM D15-72. The nip gap, mill roll speed ratio and
time of mixing were kept the same for all the mixes. The compounding was
carried out at room temperature.
2,2.2. Blend preparation

Nitrile rubber/natural rubber and nitrile rubber/epoxidised natural rubber

blends were prepared by the masterbatch technique in a two roll mixing mill. The
nitrile rubberlnatural rubber blends were denoted by No,

NSo, N70 and Nloo

where the subscripts denote the weight percentage of natural rubber in them. The

Materials and Experitnenial Methods 70

nitrile rubber/epoxidised natural rubber blends were denoted by Eo, E30, Eju, E70

and Eloowhere the subscripts denote the weight percentage of epoxidised natural

rubber in the blend.

2.2.3. Curing of the samples

The curing behaviour of the samples was followed by a Goettfert
Elastograph at an osci11ation frequency of 50 cycledmin and at a deformation

angle of 0.2". The samples were cured to their optimum cure time

(t90).

The

t90

represents the time to attain 90% of the maximum rheometric torque.

2.2.4.

Moulding of samples
Blanks cut from the uncured samples were marked along the mill grain

direction and were vulcanised at 150C in a hydraulic press having electrically

1

heated platens, under a pressure of 30 tomes/ In order to study the effect of

nature of crosslinks, mixes A, B, C and D were cured under a common

rheometric torque. This was done to minirnise the difference in the magnitude
and distribution of crosslinks between the rubber chains of the samples.

2.3.

Transport experiments
Circular samples of diameter 1.94 crn were cut from vulcanised rubber

sheets using a sharp edged steel die and were used in sorption experiments that
monitored solvent sorption gravimetrically. Initially the samples were dried

overnight in a vacuum desiccator and the original weights were taken. The
thickness of the samples was measured at several points using a micrometer
screw gauge and the average of several measurements was taken as the initial

7 1 Materials and hperimental Me!hods

thickness of the sample. They were then immersed in solvents contained in

stoppered glass bottles, which were kept at constant temperature in an air oven.

The samples were periodically removed from

test bottles, the

adhering solvent

blotted off the surface using filter paper, and the samples were weighed on an
electronic balance (Shimadzu, Libror AEU-210, Japan) with an accuracy of
f 0.001g and immediately replaced into the test bottles. The time for each
weighing was kept to a minimum of 30-40 sec in order to eliminate the error due
to the escape of solvent from the sample2 This procedure was continued until

equilibrium swelling was attained. Similar methodology has been adopted by

several researchers?-5

The mults of these experiments were expressed as moles of solvent

uptake by 1 OOg of polymer sample, Qt mol%

r Mass of solvent sorbed 1

Qt mol% =

[ Molar mass of solvent 1

Mass of polymer

00

(2.1)

The Qtvalues obtained thereby are plotted as a b c t i o n of square root of time.

2.4.

Bound Rubber Measurements

Bound rubber (BR) was measured using toluene as the ~ o l v e n tAround,
.~

0.5 g of the sample was cut in small pieces and introduced in a steel wire basket
previously weighed: the basket was suspended in 150 mL toluene for 72 h at

room temperature. Then, the basket was slowly removed from the solvent and
dried a few hours at room temperature, then for 24 h under vacuum at 40C.

Marerials and Experimenral Methods 72

Complete drying was checked by a constant final weight. The amount of BR

(in % of initial rubber content of the compound) is calculated from
(miH i t - mhxk )

BR(%I = 100 x

CPD

-(mtni, 100

where CPD is the total formulation (in phr); mi,,,,the initial weight (basket +
unextracted sample); rnk,k, the empty basket weight; and

mend,the

final weight

(basket + extracted sample), dried.

2.5.

Vapour Permeation
The vapour permeability was determined at room temperature by

measuring the weight loss of small vials filled with solvents and tightly closed by
a membrane of ~150-pmthickness of the individual polymers

and blends. The

weight loss of vapour through the membrane with time is noted7.Afler a time Iag

due to saturation of the membrane with vapour, the weight loss is linear with
time. The weight loss is proportional to time, area of the membrane and pressure

inside and outside of the vials (it can be considered zero outside of the vial), and
is inversely proportional to the thickness of the membrane, The proportionality

coefficient is the permeability.

2.6.

Gas Permeation
Permeabilities of pure gases N:! and 0

were measured using the constant

pressurelvariable volume method. A schematic representation of the gas

permeation apparatus is given in Figure 2.1.

73 Muferials and Experimenlal Methods

A - gas cylinder; B - line regulator; C - test cell;

D - pressure gauge; E micro valve; F - mercury flow meter; G- sample

Figure 2.1. Schematic representation of gas permeation apparatus

The cavity of a test cell (C), maintained at a constant temperature, is

divided by a disc test piece (G) into a high-pressure and a low (atmospheric)
pressure side. The twt cell was wnstructed of stainless steel. The effective area inside
the cell was 3.14cm2. The gas permeated h m the active membrane was passed
through the supporting medium of porous stainless steel plate. Two O-rings were used
as the sealing agent.

The high-pressure side is connected to a constant pressure gas

cylinder (A). The gas permeates into the low-pressure side (atmospheric pressure),

which is of a low volume and connected to a capillary mercury flow meter (F) for
measuring the permeated volume.
The permeability of NBR, NR and ENR and their blends to pure nitrogen
and oxygen were determind at 30C. The feed side pressure of the gases was 35 Psi.

The permeant side was maintained at atmospheric pressure.

Materials and Experimental Methods 74

Gas permeability was calcdated using the relation8

where (dV/dt )is the steady-state displacement of a mercury drop in a flow meter,
A is the membrane area, 1 is the membrane thickness, andpl andpz are the feed

side and permeate side pressure, respectively.

2.7.

Blend Morphology
Ebonite methodgwas used to investigate the morphology of elastomer blends

in which the preferential reaction of one of the rubber phases with sulphur and zinc

oxide effects a large increase in its electron density. The reaction medium for the
ebonite treatment consists of molten sulphur/accelerator (N-cyclo hexyI-2-benu,

thiazyl sulphenamide)/zinc stearate in the weight ratio 90/5/5. Small pieces of the
samples were cut and immersed in the molten sulphur mixture for 8h at 120C.

The excess sulphur was carefully scrapped off from the outer surface before thin
sections were cut for SEM observations using a Phillips (Netherlands) model

scanning electron microscope operating at 10 KV. The dimensions of the

dispersed phase were calculated from the SEM photomicrographs by considering
more than 300 domains. The size characteristics of the dispersed phase
(

En,D,, 5.and D,)

and its distribution (poly dispersity index values) in the

different blend compositions are calculated using the equationsI0

75 Materials and Experimental Methods

Number average diameter,

Weight average diameter,

Surface area average diameter

Volume average diameter,

where Ni is the number of particles having a diameter Di,

Poly dispersity index (PDI) which is a direct measure of size distribution

of the dispersed phase is calculated as

PDI = D,/&
2.8

Dynamic Mechanical Analysis

The dynamic mechanical properties of the blends were measured using a

Polymer Laboratories (MK 111) viscoelasticmeter. Compression moulded samples

of dimensions 5 x 0.5 x 0.05cm3were used for testing. The temperature rmge

used was from -70 to 30' C .

Murerials and Experimenml Methods 76

2.9

Mechanical Properties
Tensile testing of the -mples under unswollen and swollen conditions was

done at 2 9 C according to ASTM D 412-98 test method using dumb bell shaped test
pieces at a crosshead speed of 500 mrnlrnin using a Universal Testing Machine, TNE
Series 9200 (Fuels Instnunents and Engineering Pvt. Ltd.).

Tear resistance was carried out as per ASTM method D 624-98; unnicked, 90"
angle test pieces were used. The samples were cut from the vulcanised sheets parallel
to the grain diition. The test was carried out on U n i v d Testing Machine (TNE

series 5T). The sped of extension was 500 mm per minute and the temperatwe of
testing was 28 f 2C. Tear resistance has been reported in kN/m.

Tear Strength (Nlmrn) =

Ultimate Load (N)

Thickness (mm)

2.10 References
1.

T. A. Riddick and W, B. Bunger, in Techniques in Chemistry, Vol. 2 (3d

edn.) Wiley-Interscience, New York, 1970.

2.

G.Unnikrishnan and S. Thomas, Polymer, 35,5504 (1 994).

3.

M. Franson and N.A. Peppas, J. Appl. Polym. Sci., 28, 1299 (1 983).

4.

S. B. Harogoppad and T. M. Aminabhavi, Macromolecules, 24, 2595

(1 99 1).

5.

Y.D. Moon and Y.M.Lee, J. Appl. Polym. Sci., 51,945 (1994).

6.

J.L.LeblancandA.Staelraeve,J.Appl.Polym.Sci.,53,1025(1994).

7.

G.Geuskens, 5. Macrornol. Sci. Phys. B 35 (3 & 4), 579 (1 996).

77 Materials and Erperimental Methods

8.

A. Morisato, H. C . Shen, S. S. Sankar, B. D. Freeman, I. Pinnau and

C. G. Casillas, J. Polym. Sci. Part B. Polym. Phys., 34,2209 (1996).

9.

G . Gillberg, L. C . Sawyer and A. L. Promislow, J. Appl. Polym. Sci. 28,

3723, (1983).
10.

A. D. T. Gorton and T. D. Pendle, NR Technology, 12, 1 (1 98 1).