EG9601799

PREPARATION OF COMPOSITOS OF NATURAL

RUBBER LATEX (NRL) - PORTLAND CEMENT MOULD

A.M.DESSOUKI, N.H. TAHER AND H.H. EL-NAHAS

National Center For Radiation Recearch And Technology,
P.O. Box 29, Nasr City, Cairo, Egypt

ABSTRACT

The aim of this study is to prepare some polymeric moulds using Natural Rubber
Latex (NRL)- Portland Cement composites based on a delayed-action mechanism.
Factors affecting the preparation process such as concentration, mixing percentage,
additives and their effects on what is regarded as a delayed-action coacervant
combination was studied. Composites of Natural Rubber Latex (NRL)- Portland Cement
would were prepared as two separate parts. The stabilized Natural Rubber Latex (NRL)
100 parts with hydroxy ethyl cellulose (HEC) 2 parts as stabilizer and a delayed - action
coacervant (sodium meta silicate as a delaying agent) 5 parts on one hand and the dry
blend of cement 65 parts soluble in 65 parts of water as a paste on the other hand, were
mixed thoroughly on the site. (HEC) was added to the rubber latex to prevent the
coagulation of the rubber latex with the electrolyte (sodium meta silicate) present in the
rubber mixture. Two kinds of stabilization occurred in the rubber part, namely steric
stabilization and the stabilization against the electrolyte.
The effect of delayed - action coacervant (sodium meta silicate) on the initial setting
time of rubber - cement mould showed that the moulding process did not occur at
sodium meta silicate concentration less than 2.66 parts per 100 parts of rubber latex
(phr) and the optimum concentration used was 5% parts of rubber latex. It was observed
that the addition of a delaying agent (sodium meta silicate) to the rubber part enhanced
the delaying mechanism in the time needed for the moulding process, while the addition
of the delaying agent to the cement part did not have any effect on retardation of the
moulding process. Chemical coacervants function mainly by reducing the £ potential
which is associated with the electrical double layer surrounding the latex particle. This
reduction may be brought about in at least three distinct ways which take place in the
system studied.

270
 REFERENCES

1. M i l . Rao, K N . Rao. II.T. Lakhande and M.D. Tcli, J. Appl. Polym. Sci., 33,

2707,(1987).

2. N i l . Tahcr, A.M. Dcssouki and F.I I. Khalil, Radiation Phys. Chcm., 36, 785,

(1990).

, L I I. Sperling, Introduction to Physical Polymer Science, John Wiley&Sons,

New York (1986).

4. J. Wilson, "Radiation Chemistry of Polymers, monomers and plastics", Marcel

Dekkcr, Inc., N Y . P. 483, (1974).

5. FIT. Lokhande, M.D. Teli, K.N. Rao and M i l . Rao, J. Appl. Polym. Sci., 29,

1843, (1984).

6. S.Sankholkar and P C . Deb, J. Appl. Polym. Sci., 39, 1681, (1990).

~. N.M. El-Savvy, E.A. Ilegazy, A.M. Rabie, A. I lamed and G A Miligy, Polym

International, 33, 285, (1994).

8 J. Biandrup and 13.11. Immcrgut "Polymer Handbook, John Wilcy&Sons, New

York Chapter 11.224,(1966)

269
 INTRODUCTION

An important application of rubberized moulds is the ability of these compositions to

take up small relative movements which can be used in constructing materials as in
expansion joints, crack's rilling materials, blocks for road-facing, water proof paint and
soil injection... etc. A further application in waste disposal, where the important
advantage offered by mbber-cement composition moulds which can be resistant to
cracks, conosion, humidity and land trembling 0»2).

Rubber-cement flooring compositions have been exploited to the full in the jointless
surfacing of ships deckings, and as subfloors for laying of tiles in ships. The ability of
these compositions to produce a material in which the rubberized characteristics
predominated and the ability to resist corrosion by sea-water, have all contributed to
successful application in this way P ) .

Rubber-cement flooring compositions offer several distinct advantages over

straightforward concrete floors. In appearance and feel they are more elastic and more
slip-resistant. They lack the hard, cold feel which is associated with concrete. They are
durable, and can be applied in continuous, jointless layers of various and variable
thickness. They adhere very well to a variety of substrates, and this property makes them
useful for the leveling up of old, uneven floors (4*6).

The aim of this work is to prepare some polymeric moulds using Natural Rubber
Latex (NRL)-Cement composites based on a delayed action mechanism. Factors
affecting the preparation process such as concentration, mixing percentage, additives and
their effects on what is regarded as a delayed-action coacervant combination will be
studied.

271
 The characteristics of the materials used in this study are described in Table I.

TABLE I
Characteristics of Compounding Ingredients

- Ordinary Portland Cement supplied by Helwan Cement Co., Egypt

- Natural rubber latex (NRL) (TOPTEX), Malaysia.
Hydroxy ethyl cellulose (Cellosize) supplied by Union Carbide Corporation,
(U.S.A).
Delayed-action coacervant (VEGOMET) supplied by Rodenas & Rivem-Italy.
- Calcium carbonate from El-Nasr Phosphate Co. Egypt.
- Preservative Actidde (BX) supplied by THOR CHEMICAL INTERNATIONAL
LTD., England.
Antifoaming agent was used without further treatment.

Sample Preparation
The preparation of the moulds was carried out in the following way : a) all the
ingredients were accurately weighed, b) the stabilized latex on the one hand, and the dry
blend of cement and filler soluble in water on the other, are mixed throughly on the
cavity used, either manually or using a mechanical mixer.
The following precautions were taken into consideration :
a) The composition was applied as soon as possible, the time available for moulding
was limited to between 30 minutes and 1 hour.
b) The actual rate of setting depends upon the concentration of the ingredients mixed.
c) The dry blend of cement and filler soluble in water sholuld be added to the
stabilized NRL and not the reverse.

Equipment
Vical apparatus was used for determination of the initial setting time.

272
 The measurements of tensile strength (Tb) and elongation percent (Eb) at break were
carried out using an Instron (Model-1195), England, at crosshead speed of 50 mm/min.
The tensile strength and percent elongation were calculated as follows:
Load at break (kg)

cross-sectional area of the dumbell shape (cm2)

Eb (%) = x 100

Where L ~ the length of the sample at the moment of rupture,

Lo = the distance between the two jaws, i.e. the length of the
necked part.

Compression set was determined to obtain the residual strain in a latex mould test
piece after it has been held under compression to a given extent for a given time and then
allowed to recover for a given time, the temperature being held substantially constant
during the test. The result is calculated as the difference between the original thickness of
the test piece and that after recovery, expressed as a percentage of the initial applied
compression.

Shrinkage properties were tested by a liquid displacement method. Water uptake

measurements were observed by using the clean and dried samples of known weights
which immersed in distilled water for 24 hr. at 25°C. The samples were removed,
blotted by absorbent paper and quickly weighed. The water uptake percent was
calculated as follows:

(W 2 - W,) x 100
Water uptake (%) =
W,
Where
Wj and W2 represent the weights of dry and wet samples, respectively.
Conductivity measurements were carried out using a Multi-Mega Ohm meter- MOM
11 (WTW Instruments, Germany). The electrical conductivity of the sample was
determined by measuring the electrical resistance and the following equation was used.

273
 a = — ~ ohm* cm-1
R.a

L =s The thickness of sample (cm)

a = (n r2) is the area of the sample surface (cm2)
R = ohmic resistance (ohm).

RUSULTS AND DISCUSSION

Preparation of rubber-cement mould

Typical latex-cement compositions comprise a mixture of stabilized latex, a cement

(which may be either Portland or Alumnious) and fillers. The final composition usually
has a rubber content in the region of 10 to 50%. Such compositions must obviously be
made up as required. The stabilized latex on the one hand, and the dry blend of cement
and filler in water as paste on the other, are mixed thoroughly on the site, either manually
or using a mechanical mixer. The composition is then applied as soon as possible, the
time available for moulding is limited to between 30 minutes and 1 hour, sicne setting,
commences at once. The actual rate of setting depends upon several factors, and the least
important of which is the temperature.

Table (2): Typical formulation of the prepared moulds

Basic composition Additives Condition of Period Time to set

(Parts by weight) (Parts by weight) mix workable time hard

6 0 % N R L 100 Cellosize 2 very thin cream 30 minutes < 4 hours

O.P.C. 65 Vegomet 5

dist.water 65
where:
NRL Natural Rubber Latex
O.P.C Ordinary Portland Cement
Cellosize = Hydroxy Ethyl Cellulose (HEC)
Vegomet ~ Anhydrous sodium meta silicate
Mixing and moulding process
Two groups a and b are prepared first:
Group a
ordinary portland cement 65
dist. water 27
Group b
hydroxy ethyl cellulose soln. 40
(2 HEC : 38 H2O) by weight
sodium meta silicate anhydrous 5
natural rubber latex 100
Group (a) is added to stabilized natural rubber latex in group (b) and stirred well for
1-2 minutes, then moulded immediately in the cavity to be filled.
Table (3) Shows the specifications recorded according to the typical formulation.

Table (3) Specification for typical formulation

tensile strength 32 kg/cm2

elongation at break 550-650 %
water uptake (after 24 hours) 8-10 %
electrical conductivity 9.7xlO 12 Q 1 cm"1
shrinkage (after one week) 12-18 %
compression % of initial thickness (at one ton load) 90%

Factos Affecting The Preparation of Rubber-cement Mould :

Effect of hydroxy ethyl cellulose (HEC) stabilizer on rubber-cement mould:

The effect of adding a proper concentration of the stabilizer (HEC) to the rubber latex
part to prevent the coagulation of the rubber latex with the electrolyte (sodium meta
silicate) present in the rubber mixture was investigated. The effect of adding the stabilizer
(HEC) to the rubber-cement composition on the initial setting time of the mould is

275
shown in Fig (1). The results show that at a concentration less than 0.2 % parts of rubber
latex, no setting of the rubber-cement mould occured. After this concentration the initial
setting time increased as the concentration of HEC increased and reached its maximum
setting time at 2 % parts of rubber latex. This was followed by a slight decrease as the
concentration of HEC increased.

In the present work, two kinds of stabilization in the rubber part can be suggested
namely; steric stabilization and the stabilization against the electrolyte. Void*7* proposed
the following mechanisms for the stabilization of natural rubber latex (NRL):

a) Steric Stabilization

The protective barrier usually formed by adsorbed molecules in the interfacial region
of the colloidal particles. These "barriers" prevent the latex particles from approaching to
a critical distance at which they coagulate. It is hence assumed that amphiphilic
macromolecules, like hydroxy ethyl cellulose, which are adsorbed on the surface of
colloidal particles, could therefore confer stability to the colloidal dispersion at
electrolyte concentration high enough to cause coagulation in the absence of such
polymer.

b) Stability against electrolyte (delayed-action coacervant) addition :

Common polymeric emulsions prepared with ionic surfactants are usually senstive to
electrolytes and are more or less easily coagulated by them, depending upon the
counterion valence at least approximately. One of the potential advantages of the
nonionic HEC molecules that they hold the promise of acting as good steric stabilizers.

Effect of Delayed - Action Coacervant on Rubber - Cement Mould

The effect of delayed-action coacervant (sodium meta silicate) on the initial setting
time of rubber-cement mould was investigated and the results are shown in Fig (2). The
moulding process did not occur at sodium meta silicate concentration less than 2.66 parts
per 100 parts of rubber latex. Increasing sodium meta silicate concentration in cement
caused a slow coacervation of the rubber-cement mould. This slow coacervation in the
case of addition of sodium meta silicate to the cement part. In case of the addition of the
same amount of sodium meta silicate to the rubber part of the prepared mould resulted in

276
 0 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2
Hydroxy Ethyl Cellulose Concentration, phr (parts of 100 part of rubber latex
Fig (1): Effect of (HEC) stabilizer concentration on initial setting time
of rubber - cement mould.

CD
•H 3

•H

4
0)
CO

No Setting
0
0 2 4 6 8 10
1 -—in cement part— I in rubber part -—
Sodium meta silicate concentration, phr
Fig (2) Effect of sodium macta silicate concentration on initial setting time
of rubber - cement mould.

277
a big increase in the initial setting time. So, it follows that the addition of a retarder
(sodium meta silicate) to the rubber part enhanced the delaying mechanism in the
moulding process than to the cement part.

As well known, portland cement contains mainly calcium oxide which hydrolyses
slowly in water to give calcium hydroxide, which in turn interacts with the sodium meta
silicate to form a precipitate of colloidal calcium silicate. This adsorbs stabilizer from the
natural rubber latex, and encourages coacervation. Any excess of released calcium
hydroxide is effective as an accelerator of initial setting time of the rubber - cement
mould*8*.

It is known that chemical coacervants function mainly by reducing the ^-potential

which is associated with the electrical double layer surrounding the latex particle. This
reduction may be brought about in at least three distinct ways which take place in the
system sutdied :

(i) Direct interaction may occur between the added coacervant which neutralize the
electrical charge which is responsible for the existence of the double layer. Loss of an
associated hydration layer may also occur. The most usual form which such interaction
takes may be conveniently described as the "insolubilization" of the adsorbed stabilizer
which was responsible for the electrical double layer in the first place(9).

(ii) Alternatively, direct interaction of a more "physical" kind may occur between
the added coacervant and the electrical double layer. Such indirect interaction usually
takes the form of a swamping, or "compression" of the double layer by ions of opposite
polarity to that of the particle side of the double layer. It is well known that such
swamping brings about a reduction in the associated £-potential(10).

(iii) A third posibility may be discribed as an indirect interaciton between the added
coacervant and the surface phas which separates the polymer and aqueous phases. Such
indirect interaction may, for instance, occur when the coacervant causes a fine precipitate
of high specific surface area to form in the aqueous phase of the latex. This precipitate
may then successfully compete with the polymer particles for the colloid stabilizers which
are present in the system. In such cases agglomeration of the particles occurs because

278
they have been robbed of the stabilizers which formerly prevented them from coming
together(11).

Chemical coacervants also include substances which have slow gelation when initially
added to a latex, after the lapse of a certain time. These substances serve in retarding the
rate of gelation in case of rubber-cement mould leading to controlled coagulation. In our
study such a substance was used namely anhydrous sodium meta silicate.

Effect of Natural Rubber Latex (NRL) Content on Rubber-Cement Mould

Fig. (3) shows the effect of natural rubber latex content on the initial setting time of
the mould. The moulding process did not occur below a NRL content of 33, after which
an increase inthe rubber content resulted in a gradual increase in the initial setting time of
the mould. Increasing the rubber content more than 100 resulted in a sharp increase in
the initial setting time. 100 NRL content was chosen in the present study because the
water content in the NRL (100) is the optimum amount, after which the amount of water
present will lead to more shrinkage in the Gnished product which is not desired.

Effect of Cement Content on Rubber-Cement Mould :

The cement content in the rubber-cement mould played an important role on setting
time as shown in Fig. (4). On the addition of 20 % parts of rubber latex cement to the
mould an initial setting time of 35 hours was needed and the final product was not hard
enough and the amount of free water present in the mould leads to a high percent of
shrinkage. On increasing the cement content up to 65 % parts of rubber latex imporved
the hardness and shrinkage. It is an important feature of these compositions that the
cement combines chemically with considerable proporiton of the water in the latex, and
thus there is relatively little to be lost by evaporation. An additional advantage which
occurs from the increase of cement content is the reduction in the shrinkage which
occurs during the final application. It was found that 65 % parts of rubber latex is the
optimum cement content. Increasing the cement content beyond this concentration (65 %
parts of rubber latex) lead to more stiffness and cracks which is not good for practical
applications.

279
 0 25 50 75 100 125
%NRLConcentration (by original weight)
Fig (3) Effect of natural rubber latex (NRL) concentraton on initial
setting time of rubber-cement mould

0
0 25 50 75 100
Cement Concentration, phr
Fig ( 4 ) : Effect of cement concentration on initial setting time of
rubber - cement mould.

280
 Effect of Water Content on Rubber-Cement Mould :
The effect of water content on the initial setting time of the rubber-cement mould is
shwon in Fig (5). A gradual increase in the water content resulted in a gradual increase in
the initial setting time. At 65 % parts of rubber latex water content, the initial setting
time for the rubber-cement mould was 4 hours. This water content corresponds to the
cement content in the mould (also 65 % parts of rubber latex), which is the suitable
amount of water needed. Increasing the water content more than 65 % parts of rubber
latex resulted in evaporation of the excess water which leads to more shrinkage and
resulted also more deterioration of tensile strength, elongation at break and compression
set which is not good for the practical application of the final product.

CONCLUSIONS
The effect of adding a proper concentration of the stabilizer hydroxy ethyl cellulose
(HEC) to the rubber latex part to prevent the coagulation of the rubber latex with the
electrolyte (sodium meta silicate) present in the rubber mixtures was investigated. The
results show that at a concentration less than 0.2 part of hydroxy ethyl cellulose (HEC)
added to 100 parts of rubber latex, no setting of the rubber-cement mould occurred, but
reached its maximum setting time at 2 parts of HEC which was used in this preparation.
Two kinds of stabilization occurred in the rubber part, namely, steric stabilization and the
stabilization against the electrolyte.

The effect of delayed-action coacervant (sodium meta silicate) on the initial setting
time of rubber-cement mould showed that the moulding process did not occur at sodium
meta silicate concentration less than 2.66 parts per 100 parts of rubber latex and the
optimum concentration used was 5 % parts of rubber latex. It was observed that the
addition of a delaying agent (sodium meta silicate) to the rubber part enhanced the
delaying mechanism in the time needed for the moulding process, while the addition of
the delaying agent to the cement part did not have any effect on retardation of the
moulding process. Chemical coacervants function mainly by reducing the ^-potential
which is associated with the electrical double layer surrounding the latex particle. This
reduction may be brought about in at least three distinct ways which take place in the
system studied.

281
 0)
B
H

d
•H
+->
-p
<p
CO

•H
+J
•H
d

0
0 25 50 75 100 150
Water Concentration, phr
Fig (5): Effect of (water content on initial setting time
of rubber - cement mould.

282
 The effect of Natural Rubber Latex (NRL), cement and water contents in the mould
showed that the optimum ratios are :
100 rubber: 65 cement: 65 water
The possibility of some applications of the prepared rubber-cement moulds in the field
of construction as aacks filling materials, expansion joints filler and soil injection was
suggested. Also it may be applied as tile adhesive for surfaces exposed to permanent
water conditions.

REFERENCES

1. L.H. Griffiths, Chem. & Ind., p. 578 (1974).

2. W.H. Stevens, Rub. Dev., 1(3), 10 (1984).
3. D.C. Blackley, High Polymer Latices. Chap. IV, p 241, Applied Science, England
(1966).
4. A.E. Bond, B. Pat. 369, 561 (1932).
5. J.G. Robertson, Trans. IRI, 15, 196 (1939).
6. H.J. Stern, India Rub. World, 102 (2), 37 (1940).
7. R.D. Void and M.J. Void, Colloid and Interface, Addison - Wesley, Reading, MA
262 (1983).
8. W.G. Wren, Trans. IRI, 13, 189 (1973).
9. P. Cassagne, Rev. Gen. Caout., 28, 39 (1951).
10. E.W. Madge, Trans, IRI, 28, 207 (1952).
11. K. Uhl, K. Klumpner, Angew. Chem., 53, 188 (1940).

283