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The Role of Coagulants on the

Preparation of Dipped film from
Radiation Vulcanized Natural
Rubber Latex
a a a a
N. C. Dafader , Y. N. Jolly , M. E. Haque , F. Akhtar &
b
M. U. Ahmad
a
Rubber Chemistry Laboratory Nuclear and Radiation
Chemistry Division , Institute of Nuclear Science and
Technology Bangladesh Atomic Energy Commission , P.O. Box
3787, Dhaka, Bangladesh
b
Department of Chemistry , Jahangirnagar University ,
Savar, Dhaka, Bangladesh
Published online: 23 Apr 2008.

To cite this article: N. C. Dafader , Y. N. Jolly , M. E. Haque , F. Akhtar & M. U. Ahmad

(1999) The Role of Coagulants on the Preparation of Dipped film from Radiation Vulcanized
Natural Rubber Latex, Polymer-Plastics Technology and Engineering, 38:2, 267-274, DOI:
10.1080/03602559909351576

To link to this article: http://dx.doi.org/10.1080/03602559909351576

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 P0LYM.-PLAST. TECHNOL. ENG., 38(2), 267-274 (1 999)

THE ROLE OF COAGULANTS ON THE PREPARATION

OF DIPPED FILM FROM RADIATION VULCANIZED
Downloaded by [The University of British Columbia] at 20:23 29 October 2014

NATURAL RUBBER LATEX

N. C. DAFADER,l Y. N. JOLLY,' M. E. HAQUE,',*
F. AKHTAR,' and M. U. AHMAD'

'Rubber Chemistry Laboratory

Nuclear and Radiation Chemistry Division
Institute of Nuclear Science and Technology
Bangladesh Atomic Energy Commission
P.O. Box 3787
Dhaka, Bangladesh
'Department of Chemistry
Jahangirnagar University
Suvar, Dhaka, Bangladesh

Abstract

The effect of coagulants on the preparation of dipped film with good

physical properties was studied. In order to optimize various parameters
like coagulant concentration, latex concentration, and former dipping
time in latex and coagulant, the effect of coagulant on the physical prop-
erties of radiation vulcanized natural rubber latex film was evaluated.
Calcium nitrate, calcium chloride, and ammonium nitrate were used as
the coagulant by dissolving either in water or ethanol. Calcium nitrate
solution was found to be the best one among the coagulants used.

Key Words: Coagulant; Latex; Film; Calcium nitrate; Calcium chloride;

Properties.

*To whom correspondence should be sent. Fax: 800-2-863051. E-mail: inst@bangla.net

267

Copyright 0 1999 by Marcel Dekker, Inc. www.dekker.com

 268 DAFADER ET AL.

INTRODUCTION

Rubber film made from radiation vulcanized natural rubber latex (RVNRL)
has several advantages over conventional latex. These are (a) carcinogenic n-
nitrosoamine, (b) low cytotoxicity, (c) less evolution of sulfur dioxide on
burning, (d) transparency, and (e) softness, and so forth (1). RVNRL has a
wide range of applications, among which dipped goods are significant. The
dipped products play a major role in the latex industry. The dipped goods
cover about 60% of all natural rubber latex usage. Among the products, vari-
ous types of rubber gloves (household, surgical, etc.), balloons, and contra-
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ceptives are important.

Coagulants have a significant role in the preparation of dipped goods from
natural rubber latex. Kartowardoyo and Sundardi (2) and Ridwan et al. ( 3 )
compared the properties of coagulant-dipped film with straight dipped film
using calcium nitrate in a water-ethanol mixture and found that the coagulant-
dipped film possesses better tensile properties. On the other hand, Gazeley and
Pendle (4) showed in their preliminary experiment that by using 40% calcium
nitrate in water as the coagulant, the response to pickup versus time of dwell
is similar to the sulfur vulcanized one but a little slower, and the tensile prop-
erties are good enough, having a slightly lower tensile strength than that of
cast film. Saito et al. ( 5 ) produced rubber gloves using 10% aqueous calcium
nitrate solution as the coagulant and obtained a higher tensile strength and
cross-linked density than those of cast film. Hein et al. (6) used calcium chlo-
ride as the coagulant and obtained hand gloves having 22-25 MPa tensile
strength. Makuuchi et al. (7) used calcium salt in ethanol as the coagulant and
prepared hand gloves suitable for use in handling radioactive-contaminated
substances. They pointed out that the acid resistance of these gloves are poor.
Manshol et al. (8) used calcium nitrate in the mixture of water and methylated
spirit in the manufacturing process of balloons from radiation vulcanized film.
The present work states the effect of various coagulants (e.g., calcium nitrate,
calcium chloride, etc.) on the preparation of dipped film from radiation vul-
canized natural rubber latex and evaluated the optimum condition of various
parameters for preparing a dipped film of good physical properties.

EXPERIMENTAL

The field latex was concentrated by a centrifuge machine, model SPL-100

(Saito Separator Limited, Japan), and was preserved with ammonia. The latex
concentrate was irradiated by gamma rays from a source of CO-60 at room
temperature with 5 phr n-butyl acrylate (n-BA) as the sensitizer. n-BA was ob-
tained from Kanto Chemical Co. Inc. (Japan). The coagulants used were cal-
cium nitrate tetrahydrate and calcium chloride (BDH Chemical Ltd., Eng-
 COAGULANTS FOR FILM FROM RVNRL 269

land), and ammonium nitrate (Riedel-de Haen, Germany). Water and 95%
ethanol were used separately as solvents for the coagulant solution.
A long (35-cm) glass tube was used as the former for the preparation of rub-
ber film. At first, the glass tube was cleaned and immersed in coagulant solu-
tion, taken out, and dried in air. Then the dried tube was immersed in irradi-
ated latex and taken out slowly after a certain length of time. The latex-coated
former was dried in air. The dipped rubber film thus formed was separated
from the former and leached in water for 24 h. The leached film was dried in
air until transparent. Then, the film was heated at 70C for 1 h. The irradiated
latex was cast on a raised-rimmed glass plate to make a sheet. Then, the cast
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film was dried and leached. The leaching, drying, and heating of the cast film
was carried out using the same procedure as for the dipped film. The tensile
properties of the films were measured by using a Instron testing machine,
model-101 1 (England), interfaced to a personal computer.

RESULTS AND DISCUSSION

In Table 1, the physical appearances of dipped films prepared by using vari-

ous coagulants are described. It is found that uniform rubber films can be pre-
pared by using both aqueous and ethanolic solutions of calcium nitrate and
calcium chloride as coagulants. The film surface obtained by using ammo-
nium nitrate was not uniform. Thus, it is not suitable for use as a coagulant for
preparing a good rubber film. The physical appearances of dipped films ob-
tained from aqueous solutions of calcium nitrate and calcium chloride as co-
agulants are good and possess normal rubber color.
It is evident that calcium nitrate and calcium chloride are suitable for
dipped film preparation. Thus, optimum conditions of various parameters
were found by using calcium nitrate. Then, calcium chloride was used for
comparison of the effects of these two coagulants. Table 2 shows the effects
of the concentration of calcium nitrate and dipping time of the glass former in
coagulant solution on the thickness of rubber film. Both water and ethanol

TABLE 1
Physical Appearances of the Dipped Films Prepared Using Various Coagulants
Physical appearances of the films
Chemicals used
as coagulants Aqueous solution Ethanol solution

Calcium nitrate Film with uniform surface obtained Same as aqueous solution
Calcium chloride Film with uniform surface obtained Same as aqueous solution
Ammonium nitrate The film surface not uniform Same as aqueous solution
 270 DAFADER ET AL.

TABLE 2
Effect of Dipping Time of Former in Various Concentrations of Calcium
Nitrate in Water and Ethanol on the Thickness of Dipped Film
Thickness (mm) of film at the calcium nitrate concentrationsof

Dipping time 15% (wlv) 20% (WIV) 25% (wlv) 30% (wlv)
in Ca(NO&
solution (sec) Water Ethanol Water Ethanol Water Ethanol Water Ethanol
~ ~ ~~ ~~~ ~ ~

50 0.109 0.130 0.141 0.155 0.153 0.165 0.175 0.175

60 0.110 0.135 0.143 0.160 0.160 0.160 0.176 0.180
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70 0.114 0.141 0.144 0.156 0.162 0.170 0.174 0.177

80 0.112 0.138 0.150 0.158 0.156 0.173 0.171 0.184

Note: Total solids content (TSC) of latex = 50%;dipping time in latex = 50 sec.

were used as solvents for the preparation of coagulant solutions separately. It

is found that there is a little change of thickness with the change of dipping
time of the former into the coagulant solution. However, this change is in-
significant. But with increased concentration of the coagulant, the thickness of
the rubber film increased significantly. Because with a higher concentration,
a thicker layer of coagulant is formed on the glass former than with a lower
concentration, a thicker rubber film is obtained with the concentrated coagu-
lant solution than with the dilute solution in both water and ethanol. It is also
found that the thickness of rubber film prepared with an ethanolic coagulant
solution is higher than that of rubber film with an aqueous coagulant solution.
Table 3 shows the effects of the concentration of calcium nitrate and dip-
ping time of the glass former in calcium nitrate solution on the tensile strength
of rubber film. It is observed that there is no effect of the dipping time of the
glass former in the coagulant on tensile strength of dipped rubber film. How-
ever, with the increased concentrationof coagulant, the tensile strength of rub-

TABLE 3
Effect of Dipping Time of Former in Various Concentrations of Calcium
Nitrate Solution on Tensile Strength of Dipped Film
Tensile strength (MPa) of film at the calcium nitrate concentrations of

Dipping time 15% (wlv) 20% (WIV) 25% (wlv) 30% (wlv)
in Ca(NO&
solution (sec) Water Ethanol Water Ethanol Water Ethanol Water Ethanol

50 25.31 25.95 26.50 26.28 27.90 29.54 28.58 29.27

60 25.55 25.80 26.41 26.85 28.25 28.90 28.10 29.76
70 25.37 26.05 27.75 27.05 28.20 29.09 28.32 28.85
80 25.48 26.26 27.60 27.35 28.30 29.22 28.25 29.48

Note: TSC of latex = 50%;dipping time of former in latex = 50 sec.

 COAGULANTS FOR FILM FROM RVNRL 27 1

TABLE 4
Effect of Dipping Time of Former in Various Concentrationsof Calcium
Nitrate Solution on Elongation at Break of Dipped Film
Elongation at break (%) of film at the calcium nitrate concentrations of

Dipping time 15% (w/v) 20% (w/v) 25% (w/v) 30% (w/v)
in Ca(NO&
solution (sec) Water Ethanol Water Ethanol Water Ethanol Water Ethanol

50 900 1000 1000 1000 1000 1000 1000 1000

60 900 1000 1000 1000 1000 1000 1000 1000
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70 900 1000 1000 950 950 950 950 1000

80 900 950 1000 1000 950 950 950 1000

Note: TSC of latex = 50%; dipping time in latex = 50 sec.

ber film increased slightly, up to 25% concentration of coagulant solutions

both in water and ethanol. It is also found that the tensile strength of film is
slightly higher with an ethanolic calcium nitrate solution than that of the film
with an aqueous calcium nitrate solution.
Table 4 shows the effect of the dipping time of the former in various con-
centrations of coagulant solution on the elongation at break of dipped film. It
is evident that elongation at break varies from 900% to 1000%with the aque-
ous calcium nitrate solution within the concentrationused (15-30%) and from
950% to 1000%with the ethanolic solution. However, this variation of elon-
gation at break is not so significant.
Table 5 shows the effect of the dipping time of the former in latex on the
physical properties of dipped rubber film. Ethanol was used as the solvent of

TABLE 5
Effect of Dipping Time of Former in Latex on the Physical Properties of
Dipped Film

Dipping time Tensile Modulus Modulus Elongation

in latex Thickness strength at 300% at 500% at break
(mm) (MPa) (MPa) (MPa)
50 0.165 28.85 2.255 3.020 1000
60 0.174 29.59 2.303 4.050 967
70 0.170 29.22 3.586 5.206 983
80 0.175 29.45 3.510 5.210 1000
Note: TSC of latex = 50%; dipping time in coagulant solution = 50 sec; concentration of
calcium nitrate solution = 25%.
 272 DAFADER ET AL.

TABLE 6
Effect of Concentration of Natural Rubber Latex on Physical Properties of
Dipped Film

TSC of Tensile Modulus Modulus Elongation

latex Thickness strength at 300% at 500% at break
(mm) (MW (MPa) (MW (%I
45 0.148 29.05 2.154 2.982 1000
50 0.165 28.90 2.432 3.184 1000
55 0.215 29.10 2.732 3.453 1000
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Note: Concentration of coagulant solution = 25%; dipping time of former in coagulant solu-
tion and latex = 50 see.

the coagulant in this experiment because of its better performance. From the
result, it is found that there is no significant effect of dipping time on the thick-
ness of the film. The tensile strength and elongation at break of the film ob-
tained by dipping the former for various lengths of time are almost same. The
moduli at 300% and 500%elongations increase up to 70 sec but remain almost
the same for a further increase of dipping time.
Table 6 shows the effect of the concentration (in terms of TSC) of latex on
the physical properties of dipped rubber film. Ethanol was used as the solvent
for the coagulant in this experiment also. It is found that with an increased
concentration of latex, the thickness of film increases but tensile strength re-
mains almost same. Moduli at 300% and 500% elongations increase with in-
creased concentration of rubber latex, but the elongation at break remains con-
stant.
After fixing the parameters for preparing film by dipping in aqueous and
ethanolic solutions of calcium nitrate, the tensile properties of the film thus
obtained are compared with those of the film prepared by using calcium chlo-
ride as the coagulant under the same conditions. Table 7 shows the physical
properties of dipped rubber film prepared by 25% calcium nitrate and calcium
chloride solutions in water and ethanol, respectively. It is found that the thick-
ness of the rubber film with the calcium nitrate solution is lower than that of
rubber film with the calcium chloride solution, but tensile strength and mod-
uli at 300% and 500% elongations are higher with the calcium nitrate solution
than those of rubber film with the calcium chloride solution. Elongations at
break for all the cases are almost the same. It is also noticeable that the tensile
strength and moduli at 300% and 500% elongations are higher with ethanolic
coagulant solutions than those with aqueous solutions for both calcium nitrate
and calcium chloride.
 COAGULANTS FOR FILM FROM RVNRL 273

TABLE 7
Effect of 25 % Aqueous and Ethanolic Calcium Nitrate and Calcium Chloride
Solutions on Physical Properties of Dipped Rubber Film

Tensile Modulus Modulus Elongation

Coagulant Thickness strength at 300% at 500% at break
solutions (mm) (MPa) (MPa) (MP4 (%I
Aqu." Ca(NO& 0.150 27.90 2.437 3.184 1000
Eth.' Ca(N03)2 0.163 29.54 3.624 3.624 1000
Aqu. CaC12 0.255 24.09 2.410 2.410 1000
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Eth. CaC12 0.272 29.05 3.067 3.600 1025

Note: TSC of latex = 50%; dipping time of former in calcium nitrate and calcium chloride
solutions and latex = 50 sec.
'Aqu. = aqueous.
bEth. = ethanolic.

How much the physical properties of the cast films are affected if these
are leached in water and ethanol with and without coagulants is shown in
Table 8. It is observed that tensile strength and moduli at 300% and 500%
elongations of cast film leached in ethanolic calcium nitrate and calcium
chloride solutions are higher than those of film leached in aqueous calcium
nitrate and calcium chloride solutions, respectively. Elongations at break of
cast films leached in ethanolic calcium nitrate and calcium chloride solu-
tions are lower than those of the films leached in aqueous calcium nitrate

TABLE 8
Effect of Coagulant Leaching on the Physical Properties of Cast Film

Tensile Modulus Modulus Elongation

Leaching strength at 300% at 500% at break
agents (MW (MW (MW (%)
~ ~~

Water 26.870 1.992 2.049 1100

Aqu. Ca(NO& 27.665 2.216 2.216 1100
Aqu. CaC12 25.950 1.959 2.678 1100
Ethanol 28.750 2.268 3.402 1000
Eth. Ca(NO& 29.320 2.375 3.938 950
Eth. CaClz 29.1 1 3.156 4.356 1000
Note: Leaching time = 24 h.
 274 DAFADER ET AL.

and calcium chloride solutions, respectively. It is also found that the tensile
properties of cast film leached in ethanol are better than those of cast film
leached in water.

CONCLUSION

Both calcium nitrate and calcium chloride solutions as coagulants are suitable
for the preparation of dipped film from RVNRL. Ethanol is a better solvent
than water for the preparation of the coagulant solution. A solution of 25%
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(w/v) coagulant is found to be the optimum concentration for the preparation

of dipped rubber film from RVNRL.

REFERENCES

1. K. Makuuchi, in Proceedings of the International Symposium on Radiation Vul-

canization of Natural Rubber Latex, 89, 1990, JAERI-M 89-228, p. 91.
2. S. Kartowardoyo and F. Sundardi, J. Appl. Polym. Sci., 21, 3077 (1977).
3. M. Ridwan, F. Sundardi, M. Utama, and S. Kartowardoyo, Radiat. Phys. Chem.,
14, 747 (1979).
4. K. F. Gazeley and T. D. Pendle, in Proceedings of the International Symposium
on Radiation Vulcanization of Natural Rubber Latex, 89, 1990, JAERI-M 89-
228, p. 189.
5. T. Saito, F. Yoshii, K. Makuuchi, and I. Ishigaki, in Proceedings of the Interna-
tional Symposium on Radiation Vulcanization of Natural Rubber Latex, 89,
1990, JAERI-M 89-228, p. 207.
6. N. Q. Hein, D. Binh, V. T. Thien, L. Hai, N. T. Man, and V. T. Thanh, in Pro-
ceedings of the International Symposium on Radiation Vulcanization of Natural
Rubber Latex, 89, 1990, JAERI-M 89-228, p 260.
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Phys. Chem., 35( 1-3), 154 (1 990).
8. W. Manshol, N. Mohid, J. Hasan, and M. M. Said, in Report of the Fifth Expert
Advisory Group Meeting on Radiation Vulcanization of Natural Rubber Latex,
Malaysia, 1993 (private communication).