1-Crosslink density

Crosslinking refers to the bonds between the chains of a polymer. Usually cross
linking is done in order to achieve better mechanical properties. By reducing the
level of unsaturation, the polymer can be saved from degradation. A polymer is
immersed in a solvent at a specified temperature and change in mass or volume is
measured correspondingly.

1.1- Procedure
A 1 X 1 of the rubber was cut and weighed. An empty beaker was taken and
weighed. This rubber was then placed in beaker and weighed again. It was then
filled with toluene. The beaker was then covered. The rubber was allowed to swell
as it absorbs the toluene. After every 24 hours, the rubber sample was taken out,
carefully dried with a dry cloth and weighed. This was done until a constant weight
was achieved. The sample was the removed from toluene and dried at room
temperature for 24 hours. After that the sample was placed in a hot air oven at 80
0
C for about 7 hours. Then the sample was again dried at room temperature for 24
hours.

1.2- Calculations
By using the Flory-Rehner equation, crosslink density is measured:

Where
Ve = effective number of chains in a real network per unit volume (cross-link
density)
Vr = volume fraction of polymer in a swollen network in equilibrium with pure
solvent (0.19)
x1 = polymer-solvent interaction parameter
V1 = molecular volume of solvent (1.069 x 10-4 m3/mol)

The results are recorded in the Table 1.

Day
0
1
4
5
6
7
8
9

Weight (g)
1
1.94
2.30
2.35
2.31
0.98
0.96
0.95

Table 1 weight and volume of rubber with time

volume
0.62
1.205
1.426
1.460
1.438
0.609
0.596
0.590

 of rubber = 1610 kg/m3

X = 0.668 (for natural rubber and SBR blend)
Ve = 194 mol/m3 (cros-link density)

1.3- Conclusion
The cross-link density greatly effects the mechanical properties of the rubber. Low
cross-link densities decrease the viscosities of polymer melts. Intermediate crosslink densities transform gummy polymers into materials that have elastomeric
properties and potentially high strengths. Very high cross-link densities can cause
materials to become very rigid or glassy. The polymer is firstly observed to gain
weight and swell as it absorbs toluene, but as the number of cross-links increased,
the absorption rate decreased. During the swelling stage after the equilibrium was
reached, a decreased in weight of the swell is observed. This may be due to the
dissolution of rubber contents partly into the solvent.

2.1- Swelling index

When a cross-linked polymer is immersed in a good solvent, it will absorb a portion
of solvent and swell. The swollen gel can be characterized as a solution. The extent
of swelling depends on the forced between the polymer and solution. The free
energy of mixing will cause the solvent to penetrate into the polymer and dilute the
polymer solution. As the polymer chains in the cross-linked polymer network begin
to elongate under the swelling action of the solvent they generate an elastic
reactive force in opposite to this formation. The volumetric swelling reaches to the
steady state when two forces balance each other. [1,2]

2.1- Procedure
A weighed sample of rubber was immersed in a toluene and the container was
sealed. This was kept at room temperature. After every 24 hour, the sample was
taken out, dried and weighed. The change in the weight was recorded and plotted
against the number of days.

2.2- Calculation
Weight of sample before dipping in toluene = W 1 = 1.00 g
Weight of sample when it becomes constant = W2 = 2.30 g
Swell index = (W2 - W1 / W1) * 100
Swelling index = 130 %
From the reference to the Table 1, graph is plotted as shown:

Weight (g)
2.5
2
1.5

Weight (g)

1
0.5
0

10

Time (in days)

Figure 1, Weight of rubber with time

3-Bound rubber content

Rubber composites are reinforced by fillers such as carbon black and silica by
formation of bound rubber. Bound rubber is formed by the interactions between
rubber chains and filler particles. The filler-polymer interactions for bound rubber
involve physical adsorption and mechanical interactions.

3.2- Calculations
Rb % = Wfs W[mf / (mf +mv)] / Wt [ mr / ( mf + mr) ] *100
Wfs is the weight of filer and gel
Wt is the weight of sample
mf is the fraction of filler in compound
mr is the fraction of rubber in compound
mf = 08.40 / 29.97 = 0.280
mr = 11.21 / 29.97 = 0.374
W = 1.00 g

Wfs = 0.95 g
Rb % = 91.2 %

Ingredient
Natural rubber
SBR
Silica
Sulfur
TMTD
Zinc oxide
Stearic Acid

phr
40
30
30
2
2
2
1

Mass in grams
11.21
8.40
8.40
0.56
0.56
0.56
0.28

Table 2, Formulation of natural rubber and SBR blend

By the value of Rb % of 91.2 % calculated above reveals that the filler-rubber

interlinking is good.

References
[1].
http://www.academia.edu/11566466/Swelling_Index_Analysis_of_Therm
oset_Elastomer (last accessed on 22/4/2015, 10:00 AM)
[2].
ASTM 2765 Standard Test Methods for Determination of Gel Content
and Swell Ratio of Crosslinked Ethylene Plastics
[3].
ASTM D6814-02 Standard Test Method for Determination of Percent
Devulcanization of Crumb Rubber Based on Crosslink Density1
[4].
Sung-Seen Choi, Eunah Ko Novel test method to estimate bound
rubber formation of
silica-filled solution styrene-butadiene rubber compounds 2014.
[5].
Cambridge Polymer Group Swelling measurements of crosslinked
polymers