3*

A Study of Natural Rubber Latex - Filler Interaction

By
Clement Namal PERIS

This thesis was submitted to the Department of Chemical and Process

Engineering of the University of Moratuwa in partial fulfillment of the Degree

of Master of j c j e n c e in Polymer^Science and Technology.

U n i v e r s i t y of M o r a t u w a
Department of Chemical and Process Engineering,
University of Moratuwa,
82711
Sri Lanka.
6 2 7 I
April, 2004

82711

ii
 1. D e c l a r a t i o n b y the c a n d i d a t e

I certify that this thesis does not encompass without acknowledgement any material
previously submitted for the consideration of a Degree or Diploma in any University. Also, to
the best of my knowledge and belief it does not contain any material previously published,
written or communicated by any means by another person, institution or an organization
except where the due reference is made.

Clement-Ntrnal PERIS

2. A t t e s t a t i o n b y t h e S u p e r v i s o r s

To the very best of our knowledge, the above particulars, mentioned by the candidate are true
and correct.

Senior Lecturer. Senior Lecturer,

Dept of Chemical and Process Engineering, Dept. of Material Engineering,
University of Moratuwa, University of Moratuwa,
Sri Lanka. Sri Lanka

in
 Abstract of the study
An attempt has been made to evaluate natural rubber latex - filler interaction. 180°-peel test
of flexible to rigid joints was performed to determine the peel strength of natural rubber latex
-kaolin joints in order to evaluate the interaction of natural rubber latex with standard rubber
grade kaolin and activated one by ion exchange reaction with amino -functional derivatives.
Experimented natural rubber latex compounds were pre vulcanized with sulphur and
6 0
ionization radiation. Radiation vulcanization was performed using Co source irradiator,
originally designed for sterilization of medical products, with reduced gamma rays dose rate.
Its suitability for radiation vulcanization of locally produced natural rubber latex was
confirmed experimentally.

Obtained results showed that the peel off test device was acceptable for evaluation of natural
rubber latex -filler interaction irrespective of the vulcanization system used with latex
compound. Peel test results displayed the influence of modified fillers on the peel strength
values of tested laminates. Increased peel strength values of the samples containing modified
kaolin were attributed to better interaction of the filler with rubber polymer.

It was investigated, that facilitated interaction observed with natural rubber latex and modified
kaolin resulted in improved properties of filled natural rubber latex compounds of both
vulcanization system, and irradiated one was more susceptible within the experiment
performed. Preference in mechanical stability time, viscosity factor and tensile was given to
radiation vulcanization natural rubber latex (RVNRL).

Reinforcing effect of modified filers in natural rubber latex compounds was lower of that
observed earlier with dry rubber compounds. The reason for it could be associated with partial
deactivation of the active centres initially brought by modification the phenomenon that have
to be studied and overcome in the future. However, it is hoped that carried out research
positively contributes to the understanding the mechanism of reinforcement of rubber
polymers with fillers and development of the technologies upgrading cheap local mineral
resources to use them more beneficially in natural rubber formulation technology.

Another aspect covered by research related to development of radiation vulcanization

technology that gives a definite support for introduction to local latex based manufacturing
industries.

iv
 Acknowledgements

It is with a great honour and pleasure, I wish to pay my gratitude to my immediate

supervisors, Dr. (Ms.) Olga Gunapala and Dr. P.Y. Gunapala in giving their fullest support,
assistance, guidance and encouragement to make this study project a successful. Also, I
mention with a great respect that the comments and suggestions given by Dr. Shantha
Walpolage, the M. Sc. (Polymer Science and Technology) course coordinator effected greatly
to make this project a successful up to this extent.

It would be a difficult task if the colleagues of my working place, specially at the quality
control (compounding) laboratory at Ansell Lanka Pvt. Ltd., where the study was done, did
not give their fullest cooperation, express their valuable views, forward constructive critics
and important suggestions in this connection. Thus, I honour and appreciate their friendly
[Link], I wish to offer special thanks to Comrade Nishantha S. Perera ,designer, in
assisting me to complete the diagrams where they were necessary.

Every emblem certifying my relative success, whatever it is, reflects the precious love of my
parents that they showed me without any lack in all the time.

CNP
 Contents

Page numbers
Chapter 1 - Introduction to the Study 1-4

1.1 Introduction 1

1.2 Objective of the Research 4

Chapter 2 - Literature Review 5-38

2.1 Introduction to reinforcement 5

2.2 Factors influencing reinforcement 5 -7

2.3 Types of Fillers 7

2.3.1 Carbon black 8

2.3.2 Silica 8

2.3.3 Silicate Minerals 9

2.3.4 Kaolin and its Structural Chemistry 9-10

2.3.5 Cation exchange of Kaolinite 10-11

2.4 Fillers in latex formulation technology 12-21

2.4.1 Filled latex compounds for carpet applications 14-16

2.4.2 Fillers in latex based adhesives 16-18

2.4.3 Latex based paints 18-19

2.4 4 Moulded latex foams 19

2.4.5 Moulded goods 20-21

2.5 Radiation Vulcanization of Natural Rubber Latex ( R V N R L ) 22 - 25

2.5.1 Absence of nitrosoamines 22 - 23

2.5.2 Very low cytoxicity

2.5.3 Low emission of SO2 and less formation of ashes 24-25

2.5.4 Higher degree of transparency and softness 25

v 2.5.5 Degradability 25
2.6 Materials for the preparation of RVNRL
2.6.1 Sensitisers
2.6.2 Polyfunctional monomers
2.6.3 Monofunctional monomers
2.6.4 Latex

2.7 The mechanism of RVNRL

2.8 Radiation vulcanisation process

Chapter 3 - Experimental methods, materials and conditions

3.1 Experimental Objectives 38

3.2 The materials and other conditions

3.2.1 Latex
3.2.2 Toluene
3.2.3 Hydroxyetyl cellulose
3.2.4 Fabric
3.2.5 Sulphur dispersion
3.2.6 Activated kaolin
3.2.7 Sensitiser
3.2.8 Ammonia solution

3.3 Preperation of kaolin slurry

3.4 Preparation of sulphur cross-linked type pre-vulcanized
natural rubber latex compounds

3.5 Preparation of RVNR latex

3.6 Dosimeters

3.7 Testing the characters of two vulcanization systems of

kaolin and latex

3.8 Measurement of pH

VII
3.9 Measurement of MST 52
3.10 Determination of Total Solid Content 52
3.11 Measurement of viscosity 53-54
3.11.1 Viscometers 53-54

3.12 Investigating of tensile properties of the vulcanisates 55

3.13 Measurement of swelling ratio 55
3.14 Preparation of applicable specimens for the peel test device 56-57
3.15 Special devices used in the study - Peel test device 57-58
3.16 Testing of the specimen in the normal environment under static weight 58
6 0
3.17 Evaluating the suitability of the Co irradiator for the production
of RVNR latex with locally produced natural rubber latex 59

C h a p t e r 4 - Results a n d C a l c u l a t i o n s 6 0 - 72

6 0
4.1 Test results performed to find out the suitability of Co
irradiation facility in the production of RVNR latex with locally produced
natural rubber latex 60-63

4.2 Peel - test results 64- 67

4.3 Test results on physico-mechanical properties of
tilled natural rubber latex 68-72

C h a p t e r 5- A n a l y s i s o f t h e Results a n d D i s c u s s i o n 73-97

5.1 Discussion of the results on the establishment of suitability of

h
" Co irradiation facility at reduced gamma ray dose rate for
radiation vulcanization of locally produced NRL 73
5.1.1 Effect of irradiation dose on properties of RVNR latex 73-75

5.1.2 Effect of concentration of sensitiser n-BA on properties of RVNR latex 75-79

5.2 Discussion of the peel strength test results 80-85
5.3 Effect of modified fillers on properties of irradiated and
sulphur vulcanised natural rubber latex 86-94
5.3.1 Percentage modulus of the RVNR latex vulcanisates 94-97

VI11
Chapter 6- Conclusion of the study 98-101
6.1 Conclusions 98

6.2 Conclusion on the study of possibility of use of

60
low gamma ray dose rate C o irradiator for
radiation vulcanization of natural rubber latex 98
6.3 Conclusion on evaluation of natural rubber latex - filler interaction
based on peel test of latex - kaolin laminated samples 99-100

6.4 Conclusion on the study of the effect of

natural rubber latex - filler interaction on properties of
irradiated and sulphur vulcanized natural rubber latex 100-101

Chapter 7- Recommendations and Suggestions for Further Developments 102-105

7.1 Ability of manufacturing the RVTMR latex barrier products
using modified kaolin as non- reinforcing filler 102-103
7.2 Further developments to the research 103
7.3 Recommendations 103-105

Appendix 1- Technical data of Kaolin 106

Appendix 2- Measuring mechanical properties of vlkanisates 107-108

with a tensile piece of dog bone shape.

Appendix 3 -Irradiation process 109-111

Appendix 4 - Recommended antioxidants to use in RVNRL process 112

Appendix 5 - Viscosity measurements 113

References 114-116
 List of Figures

C h a p t e r 1- nil

Chapter 2

Figure 2.1: A model representing kaolinite crystals 10

Figure 2.2: Schematics of kaolin platelet 11

Figure 2.3: Comparison of sensitizing efficiency of various sensitizers 29

Figure 2.4: Sensitizing effect of M F M 30

Figure 2.5: Sensitizing efficiency of n - B A on R V N R L 31

Figure 2.6: A Structure of cross- links of N R with n- B A 35

Figure 2.7: Rate of hydrolysis of n- B A 36

Figure 2.8: Effect of the rate of radiation on Dv and maximum T b 37

Chapter 3

Figure 3.1: Line diagram of the laboratory scale ball mill 43

Figure 3.2: The setup and the electrical circuit diagram of the heat supplier 47

Figure 3.3: Diagram of showing the basic components of Brookfield viscometer 54

Figure 3.4: Line diagram of Zahn cup viscometer 54

Figure 3.5: Test specimen of lax - kaolin laminate 56

Figure 3. 6: Peel off test device used in the study 57

C h a p t e r 4 - nil

Chapter 5

Figure 5.1.1 : Effect of irradiation dose on tensile strength of irradiated samples 73

Figure 5.1.2 : Effect of irradiation dose on elongation at break of R V N R latex 74

Figure 5.1.3: Effect of irradiation dose on swelling index of irradiated samples 74

Figure 5.1.4: Effect of concentration of n-BA on tensile strength of R V N R latex 75

Figure 5.1.5 : Effect of concentration of n-BA on elongation at break of R V N R latex 76

X
Figure 5.1.6: Effect of concentration of n- BA on swelling index of
irradiated samples 76
Figure 5.1.7: Tensile strength of sulphur vulcanised and irradiated samples 77
Figure 5.1.8: Elongation at breaks of irradiated and sulphur vulcanised samples 77
Figure 5.1.9: 300 % modules of irradiated and sulphur vulcanised samples 78
Figure 5.1.10: 500% Modules of irradiated and sulphur vulcanised samples 78
Figure 5.1.11: Swelling index of irradiated and sulphur vulcanised samples 79
Figure 5.2.1: Peel stress versus peel speed for RVNR latex -unmodified
kaolin laminated units 80
Figure 5.2.2: Peel stress versus peel speed for RVNR latex -modified
kaolin laminated units 81
Figure 5.2.3: Peel stress versus peel speed for the sulphur vulcanized
natural rubber latex -unmodified kaolin laminated units 82
Figure 5.2.4: Peel stress versus peel speed for sulphur vulcanized
natural rubber latex - kaolin laminated units 83
Figure 5.3.1: Viscosity of sulphur vulcanised natural rubber latex
compounds filled with modified and unmodified kaolin 86
Figure 5.3.2: Viscosity of the RVNR latex tilled with modified
and unmodified kaolin 88
Figure 5.3.3: Mechanical stability time of natural rubber latex 88
Figure 5.3.4: Tensile strength of sulphur vulcanized natural rubber latex samples 90
Figure 5.3.5: The column graph showing the elongation at break of
sulphur vulcanised natural rubber latex samples 90
Figure 5.3. 6: A graph of showing 300 % modulus of sulphur vulcanised samples 91
Figure 5.3.7: A graph showing 500 % modulus of sulphur vulcanised
natural rubber latex samples 91
Figure 5.3.8: Swelling index values of natural rubber latex vulkanisates 92
Figure 5.3.9: Tensile strength of irradiated samples 93
Figure 5.3.10: Elongation at break of unfilled and filled RVNR latex 94
Figure 5.3.11: 300 % modules of RVNR latex samples 94
Figure 5.3.12: 500 % modules of RVNR latex samples 95
Figure 5.3.13: Swelling index values of RVNR latex vulkanisates 95
 Chapter 6 - nil
« Chapter 7 - nil
Appendix 2: Figure A- 2.1: Illustration of a typical dog bone sample 107

Appendix 3: Figure A-3.1: Irradiator set up 110

Figure A-3.2: Irradiator plan 111

>

Xll
 List of Tables

Chapter 1 - Nil

Chapter 2

Table 2. I: Clay slurry composition 12

Table 2.2: Pyrophyllite slurry composition 13
Table 2.3: Typical composition of talc slurry 13
Table 2.4: Typical composition of Natural latex based adhesive 16
Table 2 5: Composition for fixing ceramic tiles 17
Table 2.6: Effect of filler addition 17
Table 2.7: Effect of different polymer/polymer/filler ratios 19
on some foam properties
Table 2.8: Typical composition for casting the rigid model in plaster moulds 20
Table 2.9: Composition for making flexible casting 21
Table 2.10: Heat sensitive composition. 21
Table 2.1 1 :Combustion analysis of
latex gloves vulcanized under different conditions 25

Chapter 3

Table 3.1: Specifications of the latex used for the study 39

Table 3.2: Specifications of toluene used 40
Table 3.3: Technical and physical data of sulphur dispersion used 41
Table 3.4: Formulation of the control sample 45
Table 3.5: Formulation of NR latex compound filled with unmodified kaolin 45
Table 3.6: Formulation of natural rubber latex compound
filled with modified kaolin 46
Table 3.7: Formulation of the test ample for the preparation of RVNR latex 49

Table 3.8: Formulation for RVNRL with unmodified kaolin 50

Table 3.9: Formulation for RVNRL with modified kaolin 50

Xll!
Table 3.10: The types of latex -kaolin laminates 57
Table 3.11: Components of the laminated test samples
for peel-off experiment 58

Chapter 4

Table 4.1.1: Properties of RVNR latex compounds 60

Table 4.1.2: Properties of control sulphur vulcanization natural rubber latex 61
Table 4.1.3: Effect of concentration of n-BA on tensile properties of
RVNR latex films 61
Table 4.1.4: Effect of concentration of n-BA on
percentage swell of RVNR latex films 62
Table 4.1.5: Effect of absorbed dose rate on tensile properties of
RVNR latex 62
Table 4 .1.6: Effect of absorbed dose rate on percentage swell of
RVNR latex films 63
Table 4.1.7: Properties of controlled sulphur vulcanized
natural rubber latex sample 63
Table: 4.2.1 Results of peel-test of
RVNR latex film-unmodified kaolin laminated units 64
Table 4.2.2: Results of peel-test of
RVNR latex film - modified kaolin laminated unit 64
Table 4.2.3: Results of peel-test of sulphur vulcanized
natural rubber latex film -unmodified kaolin laminated units 65
Table 4.2.4: Results of peel-test of sulphur vulcanized
natural rubber latex film - modified kaolin laminated units 65
Table 4.2.5:Peel stress and peel speed, at which RVNR latex film
was peeled off from unmodified kaolin ground 66
Table. 4.2.6:Peel stress and peel speed, at which RVNR latex
film was peeled off from modified kaolin ground 66
Table 4.2.7:Peel stress and peel speed, at which sulphur vulcanized
natural rubber latex film was peeled off from
unmodified kaolin ground 67
Tables 4.2.8:Peel stress and peel speed, at which sulphur vulcanized
natural rubber latex film was peeled off from
modified kaolin ground 67

XIV
 Table 4.3.1:Properties of R V N R latex compounds,

tilled with unmodified kaolin 68

Table 4.3.2:Properties of R V N R latex compounds,

filled with modified kaolin 69

Table 4.3.3:Properties of sulphur vulcanization natural rubber

latex compounds, filled with unmodified kaolin 69

Table 4.3.4:Properties of sulphur vulcanisation natural rubber

latex c o m p o u n d s filled with modified kaolin 70

Table 4.3.5:Results of Tensile test of R V N R latex films

filled with unmodified and modified kaolin samples 71

Table 4.3.6:Results of tensile test of sulphur vulcanized

natural rubber films filled with unmodified and modified kaolin 71

Table 4.3.7:Swelling index values of R V N R latex films

tilled with unmodified and modified kaolin 72

Table 4.3.8:Swelling index values of sulphur vulcanized natural rubber latex

films filled with unmodified and modified kaolin 72

Chapter 5 -

Table 5.1 : Peel strength values of natural rubber latex - kaolin laminated units

C h a p t e r 6 -Nil

C h a p t e r 7 -Nil