we 9

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\)“\qf_R$lTy(/0%

Cg ,

HEWOF
NOVEL APPLICATIONS ‘P CAS \ .'.5Y

SHELL LIQUID IN THE PO LYMER FIELDII Y"~ **

Thesis submitted to the

COCHIN UNIVERSITY OF SCIENC E AND TECHNOLOGY

in partia[fu[fi[ment Qf t/ie requirements

for tfie awarzfqf t/ie degree qf
DOCTQR UP PHILQSQPHY
under the
FACULTY ()F TECHNOLQGY

by
MARY LUBI. C.

DEPARTMENT OF POLYMER SCIENCE AND RUBBER T ECHNOLOGY

COCHIN UNIVERSITY OF SCIENCE AND TECHNOLOGY
Kochi-682022, INDIA
January 2007
 Dqurtlnnt of Polymer Science and Rubia Teckology
Cochin Univcsily of Scince nil Te&ology
Kocl|i- 682022, India
Dr. ByTl|o||m Ihaclil Pnone: 0484 257923 (OH)
B.5c. Eng, MTecn., Pn.o o4a4 2331425 (Res)
Reader E-Mail: ethicniI@c|sIt.ac.in

Date: 30"‘ January 2M7

CERTIFICATE

This is to certifiv that the thesis entitied "Nowlqfifians jcnbwi

shfllipiin sbpnbtrfifl "' which is being subniittedly.Mary Llbi C.
in partialfizlfilrnent of the requi rernents jbr the award ifthe dqree of Doctor
QfPhilos ophy, to the Cochin Ohiversity qf Science andTecbid@', Rbchi-22
is a record of the bonqfide research work carried out by her under rny
guidance and supervision, in the Department qfPo{yrner Science ardliibéer
Technology, Cochin~682 022, and no part of the work reported in the thesis
has been presentedfor the award qfany degreefrorn any other institution.

Dr. Eb; llamas Tluclnil

Supervising Teaches
 DE CLARATION

I hereby declare that the work presented in this thesis entitled “Novel
applications of cashew nut shell liquid in the polymer field” is based on
the original research work carried out by me under the guidance and
supervision of Dr. Eby Thomas T hachil, Reader, Department of Polymer
Science and Rubber Technology, Cochin University of Science and
Technology, Cochin- 682 022 and no part of the work reported in this thesis
has been presented for the award of any degree from any other institution.

Kochi-22 Mary Lubi C.

30m January 2007
 CONTENTS

Preface

Abstract

CHAPTER l Introduction and literature survey

CHAPTER 2 Synthesis of CNSL resins.

CHAPTER 3 Development of CNSL based adhesives

CHAPTER 4 Ageing studies on rubbers modified by

CNSl- phenol- hexa resin

CHAPTER 5 Development of particleboard

CHAPTER 6 Conclusions

List of abbreviations and symbols

List of publications

* Detailed contents are given at the beginning of each chapter

 PREFACE

Cashew nut shell liquid (CNSL) occurs in the soft honeycomb of the shell of
the cashew nut. It is a byproduct of the cashew nut processing industry. CNSL
contains mainly four components: cardanol, cardol. anacardic acid and 2-methyl
cardol. Components of CNSL are phenolic in nature. lt is a feasible natural
alternative to petrochemically derived phenol.

The thesis consists of six chapters. First chapter consists of

introduction and literature review. Synthesis of CNSL- hexa resin, characterization
of the synthesised resin and the effect of P: F ratio and CNSL: P ratio of the resin
on the properties of the synthesized resin are covered in the second chapter. Study
of the adhesive properties of CNSL based resin in combination with neoprene
rubber is included in the third chapter. The effect of varying the stoichiometric
ratio between total phenol and formaldehyde and CNSL: phenol ratio of the resin,
resin content, choice and extent of fillers and adhesion promoters in the adhesive
formulation is studied. The effect of incorporation of the resin on the ageing
properties of various elastomers is outlined in the fourth chapter. CNSL as such
and resins with different phenol: formaldehyde ratios and CNSL: phenol ratios at
different concentrations are incorporated into elastomers and the mechanical
properties are determined. Effect of moulding conditions and stoichiometry of the
resin on the properties of particleboard made from CNSL- formaldehyde resin is
described in the filth chapter. The major findings of the study are summarized in
the last chapter. List of abbreviations and symbols are given at the end of the thesis
and references at the end of each chapter.

Dr. Eby Thomas Thachil, Reader, Department of Polymer Science and

Rubber Technology, Cochin University of Science and Technology, Cochin, my
supervising teacher was the main source of encouragement and support in the
progression of this work. With profound gratitude l acknowledge my indebtedness
for his inspiring guidance, competent advice and help without which the successful
completion of this work would not have been possible.

I am extremely grateful to Dr. Thomas Kurian, Head of the Department of

Polymer Science and Rubber Technology and Dr. A.P. Kuiiakose, Dr. K.E. George
and Dr. Rani Joseph former Heads of the Department for providing me all facilities
during my research work. l express my sincere gratitude to my teachers especially
Dr. Philip Kurian and Dr. Sunil K. Narayanankutty for their help, support and
valuable suggestions throughout the course of this work. My special thanks to Dr.
Beena T. Abraham for her motivation and support.

I thank all the non-teaching staff of the Department for their assistance.
Words are insufficient to express my gratitude to Sreelatha, Jaya, Preetha, Bipin,
Joby, Rajesh and Litty for their help in completing this work.

The support and encouragement of my parents are deeply acknowledged.

Above all, I thank for the grace of the Almighty God.

Mary Lubi C.
 ABSTRACT

This research project aims at developing new applications for CNSL in the
polymer field. Cashew nut shell liquid (CNSL) is a cheap agro-byproduct and
renewable resource which consists mainly of substituted phenols. By using CNSL
in place of phenol, phenol derived from petrochemicals can be conserved and a
cheap agro-byproduct utilized.

In this study CNSL based resin is prepared by condensing a mixture of

phenol and CNSL with hexamethylenetetramine and the effect of P: F ratio and
CNSL: P ratio on the properties of synthesized resin is studied. The adhesive
properties of CNSL based resin in combination with neoprene rubber are
investigated. The effect of varying the stoichiometric ratios between total phenol
and formaldehyde and CNSL and phenol of the resin, resin content, choice and
extent of fillers and adhesion promoters in the adhesive formulation are studied.
The effect of resin on the ageing properties of various elastomers is also studied by
following changes in tensile strength, elongation at break, modulus, tear strength,
swelling index and acetone soluble matter. Crude CNSL and resins with different
P: F ratios and CNSL: P ratios are incorporated into elastomers. Lastly, utility of
CNSL based resin as binder for making particleboard is investigated.

The results show that CNSL based resin is an effective ingredient in

adhesives for bonding aluminium to aluminium. The resin used for adhesive
fonnulation gives the best performance at 45 to 55 phr resin and a total phenol:
formaldehyde of l:2.9. The resin when added at a rate of l5 phr improves ageing
characteristics of elastomers with respect to mechanical properties. The reaction
mixture of CNSL and hexa and the resin resulting from the condensation of CN SL,
phenol and hexa can be used as effective binders for moulding particleboard.
Chapter 1
INTRODUCTION AND
LITERATURE SURVEY

1.1 CASHEW NUT SHELL LIQUID

1.1.1 Composition
1.1.2 Extraction

1.1.3 Refining

1.1.4 Physical properties

1.1.5 Reactions of CNSLI

1.1.6 Applications
1.2 CNSL BASED ADHESIVES

1.2.1 Adhesives

a. lngredients
b. Elastomer based adhesives

c. Thermoset adhesives

d. Thennoplastic adhesives
e. Adhesive alloys

1.2.2 Neoprene adhesives

1.2.3 Phenolic adhesives

1.2.4 CNSL based adhesives

1.3 AGE RESISTORS FROM CNSL

1.3.1 Mechanism of ageing

1.3.2 Phenolic age resistors

1.3.3 Other age resistors

Chapter 1 i _p mi
1.4 POLYMER WOOD COMPOSITES FROM CNSL
1.4.1 Particleboard

a. Wood fillers- different forms

b. Ingredients of particleboard
c. Properties and uses of particleboard
1.4.2 Plywood

a. Ingredients of plywood

b. Properties and uses of plywood

l.4.3 Fiberboard

a. Ingredients of fiberboard
b. Properties and uses of fiberboard
1.5 CNSL BASED PHENOLIC RESIN

1.6 SCOPE AND OBJECTIVES OF TIIE WORK

REFERENCES
 i i I ntroductiori
INTRODUCTION AND LITERATURE SURVEY

This research Project aims at developing new applications for cashew nut
$heh liquid (CNSL) in the polymer field. Cashew is widely cultivated in the tropics
and eaehew "ht is e Very proteinaceous tasty product popular throughout the world.
CNSL is 3 hYPYedhet 01° the cashew nut processing industry. It is cheap, renewable
and underutilized.

1.1 CASHEW NUT SHELL LIQUID

Cashew hut Shell liquid (CNSL) occurs as a viscous liquid in the sofi
heheyeemb ef ‘he Shel] of the cashew nut. Cashew nut is the crop of the cashew
tree, Anacardium occidentale L (1) native to Brazil. The plant may grow to l2 m in
height The tree also Produces cashew apple, wood suitable for boats, charcoal etc.,
and 3 gum similar te gum arabic. Cashew nut is greenish gray in colour and is
attached to the eashew apple, which when ripe is either bright yellow or red. The
hm has two Wells er Shells, the outer one being smooth and somewhat elastic and
ehve green in e0l0ur before maturity. The honeycomb is housed between the inner
and Outer she"S- The kernel is inside the shell and is covered with a brown skin
knew“ as teem Industrial grade CNSL is reddish brown in colour. CNSL
Constitutes about 20‘25% of the weight of the cashew nut.
II:»fi.‘E~h+.‘.-'.=."N

'\" ii/’
______NL|t-Sh-all
E~ ' Testet
Kernel

Fig.1 Cashew nut

Chapter], _ _ _ g g ' *'T“" 7_ _ ____ _____ __ _,_

The main constituents of CNSL are phenolic compounds with long side
chain substitution at the meta position. These compounds give most of the
reactions of phenol and can be the basis for producing a number of polymeric
substances of wide utility in industrial applications. CNSL being cheap can be a
substitute for phenol in many applications. The use of CNSL in place of phenol is
an excellent example of conservation of a synthetically derived substance and the
utilization of a cheap agro by-product. ln the modem context, CNSL occupies a
position of importance because of its renewable nature (2). CNSL is abundantly
available in many parts of the world, such as lndia, Brazil, Bangladesh, tropical
regions ofAfriea and South America. In some ofthese regions, cashew is a popular
plantation product, while some others import cashew nuts for processing.

Demand for CNSL stems from its numerous uses in many areas.
Constituents of CNSL possess special structural features for conversion into
specialty chemicals and high value polymers. This involves substantial value
addition and the chemical transformation provides l00% chemically pure products.

lndia is the largest producer of raw cashew nuts in the world. The production
of raw cashew nuts was 95,000 MT during 2003-04. The export of CNSL from
lndia during 2003-04 was 7215 MT. Among Indian States, Maharashtra comes first
in production of cashew nuts followed by Kerala and Andhra Pradesh. Export of
CNSL from Kerala was 6784 MT during 2003-04 (3).

1.1.1. Composition

The earliest work published concerning the composition ofcashew nut oil is
by Staedelcr (4). Since then many researchers have investigated the constitution of
the oil (5-7). Naturally occurring CNSL contains mainly four components:
cardanol, cardol, anacardic acid, and 2-methyl cardol. Figure 1.2 shows the
chemical structure ofthese compounds.
 i/.
Introduction

OH OH
_,1_

\ COOH
C15H31_n HO C15H31—n

OH CH
ANACARDIC ACID CARDOL

H3C

C15H31-n HO C15H31-n
CARDANOL 2-METHYL CARDOL
Fig. 1.2 —C0mponents of CNSL

Commercial grade CNSL. contains hardly any anacardic acid because of

decarboxylation during the roasting process, which converts anacardic acid to
cardano] (8). The roasting process also leads to polymerisation, which accounts for
20-25% of polymeric substances in the oil. Crude CNSL is corrosive but becomes
less so by decarboxylation and removal of H38 during the refining process. The
effect of processing parameters on the refining ofCNSL has been studied (9).

The components of CNSL are themselves mixtures of four constituents

differing in side- chain unsaturation, namely saturated, monoene, diene, and triene.
The structures of the side chains of varying degrees ofunsaturation occurring in the
four major components of CNSL are identical. Fig. 1.3 shows the linear structures.
ClSH3]-n 2
(CH1)? CH,- cu, - cu; - cm - cu. - cn,- en, - CH; n=O
(CH2)? CH = on - en, (:11, - CH2 - CH2 - cuz - cu, n=2
(CHz)-;- Cl] = CH - CH2 - CH = cu - cu, - (:11, -CH2 “=4
(CHz)1- CH = CH - CH2- CH = Cl] - ClI2- CH = CH n:6
Fig. 1.3 Components of the side chain
Chapter I * _ _
Thus CNSL contains a total of 16 monomeric substances. CNSL is the only
naturally occurring alkenyl phenolic substance.

Paul and Yeddanapally (10) identified the components of anacardic acid as

2-hydroxy-6-(n-pentadecy1)bc-nzoic acid, 2-hydroxy-6-(n—pentadeca-8-enyl)
benzoic acid, 2-hydroxy-6-(n-pentadeca-8,11-di-eny1)ben2oic acid, 2-hydroxy-6­
(n-pentadeca-8,11,14-trieny1)benzoic acid. Table 1.1 lists the constituents 01‘
anacardic acid as determined by various techniques.

Table 1.1
Composition of the constituents of anacardic acid as determined by various
techniques (values are in wt %) (7)

Consgliuents Technique employed i

9Saturated
1 34 1‘A 41I4.3;3.6152-2-3
1 11
anacardic temp.771. 7. 7 4 31 TLC-mass A
acid crystamzation l“1-.CiUV~L"1LC-gravfi1"LC-(JLC HPLQ Spfectrometryhq

_ __.. 7.. ,._ .. __ ..

Monoene 15 38.7 38.4 38.3 133.4 18.19 25-33.3 1

1 __ __. 1. _. . ‘ . I _
Diene 44 ‘ 16.3 17.3 17.3 119.9165 17-8-32.1
Triene 37 ‘ 45.1 y 44.1 40.4 142.4 41.62 36.3-50.41
1 __ _, ._ 1 2 _1. .4.‘ 4 . , .._.
Symes and Dawson (1 1) and Cornelius (12) identified the components of
cardanol as 3-(n-pentadccy1)pheno1, 3-(n-pentadeca-8-enyl)pheno1. 3-(n-pentadeca­
8,11-di-eny1)phenol, 3—(n-pentadeca-8,11,14-trieny1)pheno1. Tzible 1.2 gives the
composition of the constituents of cardanol.
 Introduction

Table 1.2
Composition of the constituents of cardanol as determined by various
techniques (values are in wt %) (7)

Technique employed

1y d1st1llat1on
. . . 1column
11 Ofcfifdaflol
Constitu<-31118
GLC 1 5 an TLC_
Molecular 1 Argentated 1 TLC—mass
A q spectrometry "
Saturated 5.4 12.68 3.11 1.98 3.94-4.35
Monoene 1 60 1 48.5 29.5 36.1; 31.31 21.64-32.2
Diene 10 16.8 1 16.6 20.1 15.23 15.36-18.22
Triene 30.6 “ 29.3 151-2 40.6 51.47 45.23-58.9
The same group of workers also identified the components of cardol as 5-(n­
pentadecyl)l,3-benzene diol, 5-(n-pentadeca-8-eny])l ,3-benzene diol, 5-(n­
pentadeca-8,1 l-di-enyl) l ,3-benzene diol, 5-(n-pentadeca-8, I l , l 4-trienyl) 1 ,3­
benzene diol,

The composition of the constituents of cardol is given in Table 1.3.

Table 1.3
Composition of the constituents of cardol as determined by
various techniques (values are in wt %) (7)

Constituents of, Technique employed

cardgl 1 ~ V —~~ 6 —A
I, _ _
” TLC-GLC
1!

. _. ..
TLC-mass spectrometry
Lsawrated 0.3 _ 0.24 0.19-2.7
Monoene 8.1 9.6 110.74 8.43-15.15 1
P1999 121.9 25.2 20.64 24.2-28.92
_TPi@11@ 169.7 62.2 168.39 36.46-67.12
_._._..;.__— — .~-—~_...

'1“ yman (6) established the components of 2-methyl cardol as 2-methyl-5-(n­

Pentadecyl) 1,3-benzene diol, 2-methyl~5-(n~ pentadeca-8-cnyl) 1,3-benzene diol,
 _Chapter I

2-methyl-5-(n- pentadeca-8,1 1-di-eny1)l,3-benzene diol, 2-methyl-5-(n» pentadeca­

8,1 1 , 14- trieny1)l ,3-benzene diol.

The relative proportions of the saturated and unsaturated constituents of 2­

methyl cardol are shown in Table 1.4.

Tablel.4
Composition of the constituents of 2-methyl cardol as determined

_ . _ . 4 _
— ~ ~a -~ — _ - — — ._;__i_.
by various techniques (values are in wt %) (7)

Constituents of F g_ g g_ MTeC1miqueemp1°y¢gd g
. . ._ ' _ H .- _ . _ ._ ._ . 1
2' methyl Cardol ? TLC-GLC 1. TLC-mass spectrometry
Saturated 1 1.66 2.43 3.92 0.96-1.34
..Monoene
" _..
— _13.9
1 -- ._1 18.42
' 15.3
' "‘ 'Y._ T". __
' "' 1|'
'7 16.27-25.28
D1666 ‘ 18.5 20.4 L 20.15 20.56-24.36 N
I

T6666 65.0 61.5 57.5 49.82-62.2

Table 1. 5 give typical compositions of natural and technical CNSL.
Table]. 5
Phenolic composition of natural and technical CNSL (values in wt %) (7)

1 ,Cardanol
1

__ _ i _,1.2i ,___ , ii
1 Component Natural CNSL y Technical CNSI. 1
I 62.86 .
'2-methyl
Cardolcardol
11.31 11.25
, 2.04 2.08
1
\ Polymer 1 20.3 1 23.8
Anacardic acid 64.93 1 _i :4
The phenolic nature of the constituents of CNSL along with varying degrees
of unsaturation in the side chain makes it a highly polymerisable substance
amenable to a variety of polymerisation reactions. Of overriding importance,
however, is the condensation reaction with active methylenes that formaldehyde
exemplifies. This leads to a pheno1- formaldehyde type condensation.
 Introduction

1.1.2. Extraction

A process for extracting CNSL has been patented in India in September

1961 (13). Traditionally, a number of methods are employed to extract the oil from
the nuts. Often a particular region follows a technique by convention rather than by
deliberate choice. The following are the popular methods currently employed for
the extraction of the oil (6).

a. Hot oil bath method

The raw nuts are passed through a bath of hot CNSL at 180- 200°C. The
outer part of the shell bursts open and releases CNSL. About 50% of the oil is thus
recovered. This process makes the disintegration of nuts easy, without adversely
affecting the quality ofthe kernels. Improvements over this basic technique include
initial surface wetting and dipping in water at 20-250C and subsequent steam
treatment prior to exposure to the hot CNSL bath. The excess moisture content of
7-10% of the weight of the nuts causes the cells to burst, with the result that the oil
oozes into the bath. Another 20% could be extracted by passing the spent shells
through an expeller and the rest by a solvent extraction technique. The expeller oil
can be upgraded by acid washing followed by centrifugation and heating.

b. Roasting method

Sudden exposure to higher temperature from ambient is the basis of this

method. The shells are charred during this process, producing an explosive
pressure in the cellular structure, which forces the liquid out of the shell. In drum
roasting the nuts are heated at high temperature in a rotating drum and then shelled.
One variation of this method is abrading at 100-300°C for about I hour and
subsequent roasting at 400-700°C in an inert atmosphere. In yet another patent, the
nuts are first abraded and then treated with moisture and heated in an infrared oven.
Finally they pass through a high frequency electric field, where the liquid flows
out. Often this technique is employed in conjunction with an expeller, where the oil
is expelled from the shells to an extent of 90%.
Chapter 1 _ _ _
c. Miscellaneous methods

CNS]. is expelled by exposing the shell to superheated steam at temperatures

ranging from 150°C to 300°C (14). Extraction of the oil by solvents such as benzene,
toluene, petroleum hydrocarbon solvents or alcohols (I5) or with supercritical CO2
and water are other reported techniques (16). Report of a power operated cashew nut
sheller has also appeared (17).

1.1.3. Refining

Sulfides, nitrogenous materials, and minerals contained in crude CNSL

directly affect the quality of the oil. Hence CNSL is often subjected to chemical
treatment with substances such as hydrocarbon sulfates and sulfuric acid before
industrial use. Several acid treatment processes have been found to reduce the
poisoning or vesicant action. Aqueous solutions of acids such as hydrochloric acid,
sulfuric acid, acetic acid, chloroacetic acid or phosphoric acid, or acid sulfates such
as sodium hydrogen sulfate are employed for this purpose. This performs two
important functions: mineral salts of ammonium, calcium and potassium are
precipitated and there is a reduction in the content of skin vesicant present in
CNSL. The chemical treatment is accompanied by the evolution of hydrogn
sulfide. The reduction in sulfur content has been found to correspond roughly to the
removal of the agent responsible for the skin irritation. Treatment with amines or
with hydroxides of the metals of group lA or llA has been found to reduce the
cardol content.

The refined CNSL can be readily distilled under reduced pressure or

hydrogenerated, both processes leading to products with good colour stability.
Steam treatment of H2804 treated CNSL followed by distillation has been found to
deodorize the oil to a substantial extent.

Physical constants of CNSL before and afier chemical treatment are

summarized in Table 1.6 (18).
 1n_tr0ducti on

Table 1.6 (18)

Physical components of the oil before and after chemical treatment
T T A T T if T Rawoiil i Treated oil
Iodine no., Wijs l 269 Z54
L
Refractiveindex,20°C T 1.5158-1.5162 1.5212-1.5218
Specific gravity, 25°C g _ _ _ _F__g_ MAO-958 0-96 g____g g
Saponification value _" 19.6 M 29.7
Viscosity at 25°C, cp 400 435
Acety] value , 173 l 156
1.1.4. Physical properties

CNSL is dark viscous oil with a characteristic smell, quite unlike other
vegetable oils. It is opaque and when applied as a thin film, is reddish-brown in
color. It is immiscible with water but miscible with most organic solvents. CNSL
has germicidal and fungicidal properties. It is used traditionally as a cure for acne
vulgaris ofthe feet in Kerala. Table 1.6 gives some ofits physical properties.

1.1.5. Reactions of CNSL

The chemical structure of CNSL is such that it can take part in a large
number of reactions. A few reviews have appeared summarizing the known
reactions of CNSL (6, 19). The reaction schemes given in the following sections
are based on cardanol, the major constituent of CNSL.

a. Decarboxylation

OH OH
As mentioned earlier, anacardic acid decarboxylates on heating to cardanol.
Fig. 1.4 shows the chemical changes taking place during decarboxylation (I9).

.coo|-| HEAT \
C15H31-n C15H31-n
/
Fig. l. 4. Decarboxylation of CNSL.
Chapter 1

b. Hydrogenation (20)

Hydrogenation is usually carried out using hydrogen and catalysts such as

copper, nickel, palladium and platinum (Fig. 1.5).

OH OH

Cu, Ni,Pa,Pt

Fig. 1. 5 Hydrogenation of cardanol

c. Polymerisation

CNSL can be polymerized by a variety of techniques. The unsaturation in

the side chain can be the basis for addition polymerisation (21-23) using free
radicals or ionic initiators. Acids such as H2S04, HCI, paratoluenesulphonic acid
(PTSA) etc. can give polymeric products. CNSL can be polymerized using salts
such as zinc chloride, stannic chloride, ferrous sulphate, aluminium sulphate, boron
triflouride and salts of iron, cobalt, nickel, boron, chromium, lead, silver, mercury,
manganese, etc. These salts are generally used to the extent of 1-60/0.

The phenolic properties of CNSL are utilized to make condensation

polymers by reaction with formaldehyde, furfural, H~1TA, etc. (24-26). These
polymers are similar to the product of phenol and formaldehyde condensation but
shows less reactivity during synthesis and later during crosslinking. Both resole
and novolac type resins can be made.
OH OH OH
I R
~,/
i
i

R ~~/ R R r<:>
~I
:;:/ R / R
HO

R=C1sH31-n
Fig. 1.6. Resole resin made from cardanol (7)

12
 Introduction

In the presence of alkaline catalysts and with more formaldehyde, the

methylol phenols condense either through methylene linkages or through ether
linkages. In the case of resole type polymers, the structure of the final product has
been studied by Tyman (7) (Fig. 1.6). Working back from this structure and in
analogy with similar reactions for phenol the reaction scheme leading to this final

on OH
crosslinked network can be given as shown in Fig. 1. 7.

+ CH2O
-—-> R\'on
CH,OH
CH,OH
CH O

+ CHQO QH QH R
R \ CW0" / cH,0H
R -i> R + cH,o cH,0

cH,oH cH,oH
2R+R R )- +R R R
OH OH OH OH OH
CH OH CH?OH - CH? CHYOH CHPOCHQ

+
R , CH
OH
R
CH2OH 7 OH
R
OH
OH

HR
)
H’ CH2OH c on

OH OH OH OH
RRRR CWOC“? -HCHO C“? 7 >­

R=C1sHa1 -I‘!

Fig. 1.7. Polymerisation of CNSL using alkali catalysts.

13
Chapter 1

In the presence of acid catalyst and with less formaldehyde, the resin has no
reactive methylol groups and therefore is incapable of condensing with other
molecules on heating in the absence of hardening agents. To complete
resinification, more formaldehyde is added, resulting in crosslinking. The final
structure of the novolac product has also been given by Tyman (Fig. 1.8).

R.
HO * T

HO t
F2

HO e '
R=C,5H 31 -n
Fig. 1.8. Novolac resin made from cardanol (7)

It is observed that condensation of CNSL takes place at one of the ortho

positions and the para position of the phenolic ring. Condensation does not occur at
the ortho position between the side chain and the OH group. The expected reaction
scheme for the novolac product is given in Fig 1.9. This is deduced by considering
the final polymer structure and the reaction of phenol under similar conditions.

The condensation in this case is more difficult because of the im.miscibility

of CNSL and HCHO layers and the steric hindrance caused by the lengthy side
chain. Longer processing times are needed and the reaction product is a mushy,
high viscosity substance, which tends to solidify at comparatively low degrees of
polymerisation. In certain applications, a preliminary step of polymerisation
through the side chain is done before condensation polymerisation.

l4
 Introduction

CH2OH
OH on CHZOH
+
R
R

OH / CHZOH
R\ on
+ CH2O

CH2OH
on

RR +

(;|-|20|-| CHQOH

RRR R
____ </ \
HO CHZOH + H0 CHZOH HO CHPCH2 _* OH
CHZQH CHZOH C|'|2OH CH2OH
R=C1sH31 -n

Fig. 1. 9. Polymerisation of CNSL using acid catalysts.

+
Similar reactions can be conducted with hydrogenated cardanol and the
product converted to methyl ether and then oxidized with KMnO4., giving a
substituted acid. (Fig. 1.10).

OH Alkali OH CHZOH

C15}-I31 C15H31 I

I (c|-|3),_,so4

HOOC
OCH
3 (O) OCH3 CHQOH
Ra-—-——
CH
"5 3‘ KMHO4 0,443,
Fig. 1.10. Condensation of hydrogenated cardanol
followed by etherification and oxidation.
Ellapter 1 _ 4
Mishra and Pandey have investigated the kinetics of alkali catalyzed
formaldehyde condensation after thoroughly reviewing the results previously
reported by various workers (27). O'Conner and Blum have studied the thermal
stability of some formaldehyde condensate resins (28).

The structure and properties of CNSL novolac resin prepared using succinic
acid as a catalyst has been investigated (29). The synthesis and characterization of
a large number of resins using different hydroxy aromatic compounds,
formaldehyde, furfural, and substituted aromatic compounds like CNSI. in the
presence of acid and base catalysts have been studied (30, 3|).

Oxidation polymerisation using acid oxidizers such as HNO3 can also give
polymers, which have proved to be excellent for surface coatings and paper/fabric
impregnation (32). CNSL on treatment with copper, lead, aluminium etc.
undergoes polymerisation. The air drying qualities of CNSL were found to improve
by this. Enzymatic polymerisation of alkyl phenols derived from CNSL has been
carried out in a dioxan-water mixture (33).
0
When CNSI. is simply heated to 200 C or above, it undergoes
polymerisation. Cationic, anionic or oxidizing agents can accelerate the process.
Alkalis can also be used as catalysts for the polymerisation of CNSL by heat. The
first step is usually the reaction of phenolic hydroxyl with the alkali, and the
compound thus obtained acts as a catalyst for the polymerisation (19).

Mono or dialkyl sulphates in concentrations of about 2% have been used to

polymerize CNSL at about 1600C. The advantage of using alkyl sulphates is that
metal present as impurities in CNSI. are precipitated out durink polymerization
(34)

d. Sulfonation (35)

CNSL derivatives can be sulphonated to yield alkyl aryl sulphonic acid or

their metal salts. The reaction is carried out using concentrated H2804 at 108°C.
The reaction scheme shown in Fig. 1.1 1 employs hydrogenated cardanol.
 Introduction

or-| OR
C15H31 C1sH31
OR|_|
OR1 t
-|-| Q 1 + 2804
C15H31 2 \ C15H31
Zn, Ca, Ba

Fig. 1.11. Sulfonation of hydrogenated cardanol.

To prevent polymerisation during sulphonation, an aryl or alkali group is

substituted for hydrogen and the double bonds of the aliphatic side chain are
saturated by hydrogenation before treatment with the acid.

e. Nitration (I9)
Direct nitration of cardanol or CNSL leads to simultaneous oxidation and
polymerisation. By nitration of hydrogenated cardanol, 4-nitro compound and 6­
nitro compound were obtained. Nitroderivatives of cardanol are very efficient

OH OH OH
antioxidant for gasoline, mineral hydrocarbons, petroleum products and lubricating
oils (Fig. 1.12) (36-38).

I/ \C+HHNO3 +
C15H31 C15H31
15 31
wok

N02
+ H20
Fig. 1.12. Nitration of cardanol.
f. Halogenation (39)

Halogenation of CNSL can be accomplished with comparative ease. For

example, chlorine gas can be passed through CNSL dissolved in kerosene to obtain
q'i“P“"
'*_"*'—*" '1I "—
_ ,- c-—=‘ '
15% (w/w) chlorination. Chlorinated CNSL reacts with active methylenes at a
faster rate and are more flame resistant. The halogenation is accompanied by
polymerisation and thickening and a large exotherm.

OH OR
g. Etherification (40)

2 + R2804 "' 2 + H2804

C15H31 C15H31
Fig. 1.13. Etherification of cardanol.

Cardanol can be reacted with dialkyl sulphates in presence of alkalis to give dialkyl
cardanols. Fig. 1.13 shows the chemical changes during etherification.

h. Esterification (41)

Cardanol can be reacted with acid chlorides in the presence of alkalis to give
cardanol esters. Thus benzoyl chloride gives benzoyl cardanol (Fig. l.l4). Various
other esters of industrial importance have also been reported (38).
OH Alkali OCOCGHS
+ C6H5COCl cccc i__,, + HCI

C15H31 C15H31
Fig. 1.14. Estcrification of CNSL.
 I ntroducfion

i. Epoxidation (42)

Epoxidation of the phenolic group can be accomplished by the reaction of

CNSL with epichlorohydrin. The chemical changes during this reaction are shown
in Fig. 1.15. Epoxy resin can also be prepared from glycidyl ethers by reaction with
CNSL.

Q|-| O-CH2—CH-CH2 /O\

/O\
+ CH;-— CHCH2CI -____-___-4.. + N89‘
C15H31_n C15H3‘m
Fig. 1.15. Epoxidation of cardanol.

According to Kamath et al., reaction product of cardanol and phenol when

reacted with epichlorohydrin produced epoxy resin which claimed to be superior to
conventional epoxy resin (43)

j. Miscellaneous reactions

Pillai and co-workers (44-50) have investigated the phosphoiylation of

cardanol and the prospective applications of the products. Urethanes have been
synthesized from CNSL as in the case of other hydroxy compounds, by reaction
with isocyanates (51). CNSL can be converted to acetals by reaction with
compounds like dimethyl acetal in presence of acids (19). lsocyanates have been
prepared from hydrogenated cardanol (52). A20 dyes are made by the reaction of
phenols with primary aromatic amines after diazotization of hydrogenated cardanol
(53). By reacting CNSL with triethylene-tetramine, phenolic polyamines can be
prepared (54). Benzotriazole derivatives are prepared from hydrogenated cardanol
by diazotizing with aromatic amines followed by reduction. Syrenation of CNSL
resin can be done by reacting styrene with CNSL hexamine condensate (55).

1.1.6. Applications

Polymers derived from CNSL have ceflain outstanding properties which

make them unique for many applications. The most attractive aspect of CNSL as a
ghapter 1, _ _ _
starting material is its low cost. The polymer shows flexibility due to intemal
plasticization resulting from the presence of the long side chain. This long aliphatic
side chain also gives water resistance. It has low fade characteristics, which make it
a desirable component of brake lining formulations. lt is compatible with a wide
variety of polymers such as alkyds, melamines, polyesters etc. lts ready solubility
in a number of common solvents makes it a natural choice for a large number of
surface coating applications. There have been a number of reviews on the
applications of CNSL-based materials (56-82).

Consumption of CNSL by Indian Industry (Estimated) in 2003 (Mega tons)

(83)
Break linings 1200-1400
Paints and varnish 600-800
Lamination 900-1000
Foundry 400-500
a. Brake linings and clutch facings
CNSL and cardanol based resins have found extensive uses in automotive
brake lining applications as binders/friction property modifiers. CNSL polymers
are a natural choice for this application because of an excellent blend of properties
such as low hardness, abrasion resistance, longer retention of breaking efficiency,
low fade characteristics, better water repellence and low cold wear (83. 84)

Addition of friction dust gives a silent braking action, which is highly

desirable in modern times. About l2,000-15,000 tons of brake linings are produced
for use in motorcars every year in the country. With increasing use of automobiles,
there is an expanding market for brake lining applications.

-In brake lining materials, two types of CNSL products are used:
1. CNSL resin as a partial substitute for phenolic resin to reduce cost and
2. CNSL based friction material (friction dust) to modify the friction and wear
properties of brake linings­
 I ntroductiou

Modified CNSL resin can substitute phenolic resin totally and meet all the
specifications of brake linings. Additionally it improves impact properties and
reduces fade.

Friction dust is added to brake linings to modify the frictional and wear
properties of brake linings. It also provides properties similar to that of CNSL
matrix resin. Formulations for excellent fade characteristics, enhanced thermal
stability, good resistance to noise, high resistance to hygroscopy, corrosion
resistance, rust resistance and low brake noise have been reported (85-100).
Friction dust is generally prepared by crosslinking CNSL formaldehyde resin with
hexamine / parafomialdehyde and powdering the product to the required
specifications. Modified friction dust for applications in ‘hot wear’ conditions can
be prepared from modified CNSL resin.

b. Surface coatings

The chemically stable nature of CNSL, the solubility of the resin in various
solvents, the inherent hydrophobicity and chemical resistance, the film forming
nature, anti-termite, anti-microbial properties, and a high degree of unsaturation
make CNSL polymers highly suitable for surface coating applications. The
formulation and manufacture of various classes of paints based on CNSL have
been described by Ramanujam (I01).

Films of high heat resistance, corrosion resistance, excellent electrical

properties, anti-corrosive, water and solvent resistance properties, water based
coatings etc. can be formulated from CNSL. CNSL based surface coatings possess
excellent gloss and surface finish with optimum levels of toughness and elasticity.
Because of the dark colour its uses are restricted to anticorrosion primers, black
enamels, paints to prevent marine growth on structures, etc (102). Transparent
resin from CNSL that can be used as a base for paint of all colours has been
developed ( 103).

CNSL resins give excellent lacquers with decorative and protective

properties. Lacquers from CNSL have been used as surface coatings for wood,
porcelain, metal ware and so forth (I04-115). The dried film of this lacquer is
superior to ordinary oil paints in resistance against oils, grease, moisture and
4: 1 l _
chemicals. Lacquers for special applications such as screen lacquering and gold
lacquenng are prepared from CNSL.

CNSL resin based vamishes possess good insulating properties apart from
their high water repellence and low dielectric properties. Although CNSL and its
resins are highly susceptible to fire and burn easily, they can be successfully made
fire resistant by incorporating flame retardant agents chemically or flame retardant
fillers physically.

CNSL resins singly or in combination with other resins show excellent water
and weather proofing properties and can be used for protection of roofs. Shirsalkar
and Sivasamban have prepared anticorrosive paints based on CNSL, which have
been found to be suitable for ships hulls and other such applications (1 l6-l 17). The
coating withstands alkalinity normally encountered with cathodically protected
steel hulls. Rust inhibiting zinc rich primers can be prepared from CNSL. Coatings
giving tough elastic films are reported from CNSL-glycerine reaction products
(l 18).

c. Foundry

The phenolic nature of CNSL facilitates the use of resin derived from it in
place of conventional phenolic materials used in the foundry industry. The fire
retardant and ablative properties associated with the phenolic structure are
responsible for this. CNSL is being used as a substitute for linseed oil in the
manufacture of foundry core oil used as binder in foundry. CNSL resin imparts
good scratch hardness to sand cores after baking them. lt also provides resistance to
moisture and weathering, good green strength and surface finish to moulded
articles (l 19). Modified CNSL resin when used as core binder is found to improve
collapsibility of the core and enhances bench life and anti-damp behaviour in
comparison to conventional core binders (76).

d. Laminates

CNSL based resins improve the resistance to heat, the bonding with
reinforcement materials and the flexibility of laminates while reducing brittleness
and age hardening. Resins for laminated products are made from CNSL and phenol
by reaction with aldehydes. Modified phenolic resins are used for making laminates
 .l??§C‘?i7!‘.?¥'l°"

with good dimensional stability and warp resistance. Metal-polymer laminates of

high inter laminar shear strength have been developed from CNSL (I20).

e. Miscellaneous applications
CNSL forms the basic raw material for a vast number of industrially important
chemicals. Patents and reports cite a number of applications such as antioxidants,
bactericides, fungicides, disinfectants, insecticides, dispersing and emulsifying
agents, dye stuffs, ion exchange resins, surfactants, stabilizers, curing agents etc
(121-145). Lipid nanotubes can be prepared from CNSL (146). Applications of
CNSL in adhesives and rubber compounding are discussed in sections 1.2 and 1.3

1.2 CNSL BASED ADHESIVES

1.2.1 Adhesives

An adhesive is a substance that bonds two substrates by surface attachments.

Adhesives can be categorized both in temis of their chemical composition or
polymer type and their physical forms. Adhesive compositions include a number of
additives such as plasticizers, tackitiers and fillers in their formulation. To enhance
performance primers and coupling agents are sometimes employed.

Advantages of adhesive bonding are (l) they permit bonding of materials

that are impractical to join in other ways (2) possibility of joining dissimilar
materials (3) uniform stress distribution in the joints (4) enhanced environmental
protection (5) resistance to vibration and shock (5) better aesthetic appeal (6)
higher speed of production and lower cost etc.

On the other hand, adhesives can be sometimes relatively expensive, have

high temperature limitations, ofien require surface preparation and require jigs,
presses or other fixtures to hold parts in place until the adhesive cures (I47-150).

a. Ingredients

The components of an adhesive mixture are usually determined by the need

to satisfy application properties of the adhesive or properties required in the final
joint.
Chapter I _ __ _
Binder - The basic component of the adhesive formulation is the binder which
provides the adhesive and cohesive strength in the bond. lt is usually an
organic resin but can be a mbber, an inorganic compound or a natural product.
Diluent — It is employed as a solvent vehicle for other adhesive components
and also to provide viscosity control which makes a uniformly thin adhesive
coating possible.
Catalysts and hardeners — These are curing agents for adhesive systems.
Hardeners chemically combine with the binder material. The ratio of hardener
to binder sometimes determines the physical properties of the adhesive.
Catalysts are also employed as curing agents for thermosetting resins to reduce
cure time and increase the crosslink density of the synthetic polymer.
Accelerators, inhibitors and relarders- These substances control the curing
rate. Accelerators speed up the curing rate by combining with the binder. An
inhibitor arrests the curing reaction. Retarder slows down the curing reaction
and prolongs the storage or working life of the adhesive.
M0d:fi'ers- These are chemically inert ingredients added to adhesive
compositions to alter their end use or fabrication properties. Modifiers include
fillers, extenders, thinners, plasticizers, stabilizers and wetting agents.
i. Fillers are non adhesive materials which improve working properties.
strength or other qualities oftlie adhesive bond.
ii. Extenders have some adhesive properties and are added as diluents to
reduce the concentration of other adhesive components and thereby
the cost ofthe adhesive.
iii. Thinners are volatile liquids added to modify the consistency or other
properties.
lv Plasticizers are incorporated to provide the adhesive bond with
flexibility.
v. Stabilizers are added to increase its resistance to adverse service
conditions.
vi. Wetting agents promote interfacial contact between adhesive and
adherend by improving the wetting and spreading qualities of the
adhesive.
 Introduction

b. Elastomer based adhesives

These materials are based on synthetic or naturally occuring polymers

having superior toughness and elongation but lower modulus. Curing procedures
vary depending on the type and form of adhesive. These adhesives can be
formulated for a wide variety of applications, but they are generally used for their
high degree of flexibility and superior peel strength.

These adhesives are used in unstressed joints on lightweight materials. So

they cannot be considered as structural adhesives. They are particularly
advantageous for joints in flexure. Most of these adhesives are modified with
synthetic resins for bonding rubber, fabric, foil, paper, leather and plastic films.

I. Natural rubber (NR)

NR is the most widely used of all elastomers in pressure sensitive adhesives.

NR adhesives display excellent flexibility, rich initial tack and good tack retention.
The most suitable grade of raw rubber for making adhesive solutions is pale crepe.
2. Styrene butadiene rubber (SBR)

Styrene butadiene rubbers are copolymers of styrene and butadiene. They do

not have outstanding adhesive properties but are cheaper and have better heat
ageing properties than NR. SBR absorbs less water and reinforced compositions
have higher strength retention.

3. Nitrile rubber (NBR)

These materials are predominantly random copolymers of butadiene and

acrylonitrile. Usually the copolymer contains enough acrylonitrile so that good
resistance to oil and grease is obtained. The adhesive properties improve with
increasing acrylonitrile content. NBR adhesives have outstanding shelf stability
and high temperature properties. Because of the high polarity of nitrile rubbers,
they show good adhesion to surfaces such as textile, paper and wood.
crass».-,1 _
4. Butyl rubber (rm)
Butyl rubber is a copolymer of isobutylene with a small amount of isoprene.
This elastomer is non-crystallizing, has a largely saturated backbone, and is
available in a wide range of molecular weights. Butyl adhesives are mainly used in
sealants and caulks where resistance to oxidative degradation is important.
5. Chloroprene

Chloroprene is often used in contact cements. The basic components of the

adhesives are the elastomer and about 30-35 phr reactive phenolic resin. The more
rigid the rubber and complete the crystallization the shorter the open time and greater
the ultimate peel strength ofthe bond. More details are given in Section 1.2.2

c. T hermoset adhesives

Because thermosetting adhesives are densely crosslinked when cured their

resistance to heat and solvents is good and they show little elastic deformation
under load at elevated temperature. Bonds are ordinarily good to 93-260°C. Creep
strength is good and peel strength fair. The major application is for stressed joints
at somewhat elevated temperatures. Most materials can be bonded with
thermosetting adhesives, but the emphasis is on structural adhesives.
I. Epoxies

The principal epoxies used for commercial adhesives are the reaction
products of epichlorohydrin with dihydroxy compounds and include bisphenol A,
novolacs and aliphatic glycols. Novolac based epoxies have functionalitics greater
than two and sometimes over five. They give adhesives of higher crosslink density
and consequently, high heat resistance. The wide acceptance of epoxy adhesives is
based on its high adhesion to many substrates, low shrinkage and creep, ability to
formulate l00% solids and a large number of possible coreactants ("l51). Epoxies
are used to bond metals, glass, ceramics, plastics, wood, concrete and other
surfaces.

2. Amino resins

The condensation product of formaldehyde with urea or melamine is the

important members of the amino resin class. The largest application of urea
 I ntro_duch'0:1

formaldehyde resin is in bonding wood, principally in the manufacture Of

particleboard. In the furniture industry UF resin finds use as inexpensive adhesives.
Consumption of melamine resins is about 1/5 that of urea resins because of the cost
differential. Melamine resins are used where light color, resistance to solvents and
abrasion are required.
3. Polyesters

Polyester hot melt adhesives are prepared by copolymerisation of multiple

diacids or glycols. The principal use of polyester hot melt adhesives is in shoe and
textile industries. Unsaturated polyesters which require a catalytic cure are used for
the bonding of polyester substrates.

4. Silicones

Silicone adhesives are mainly used in construction industry because of their

excellent physical properties, high elongation, chemical lI1CI'lI16SS and heat
resistance.

5. Polyurethanes

Polyurethane adhesives are reactive adhesives, fully formed polymers

applied from solution or used as films and aqueous dispersions. In reactive
adhesives, the usual isocyanates used are toluene diisocyanate and diphenyl
methane- 4, 4'-diisocyanate. Depending on the molar ratio of isocyanate to OH
groups, the prepolymers may be either isocyanate or hydroxyl terminated. The
isocyanate terminated prepolymers are usually applied from solution. Curing takes
place by reaction with moisture ofien with the help of multifunctional compounds.

d. Thermoplastic adhesives

These materials do not crosslink during cure. So they can be resoftened

repeatedly with heat. Thermoplastic adhesives are not ordinarily recommended for
use over 66°C, although they can be used up to 900C in some applications. These
materials have poor creep resistance and fair peel strength. They are used mostly in
unstressed joints and designs. The materials most commonly bonded are
nonmetallic, especially wood, leather, cork and paper. Thermoplastic adhesives are
not generally used for structural applications.
Chapter] 7 _____ ‘_ _
1. Ethylene copolymers

These materials are copolymers of ethylene and vinyl acetate. The most
important ethylene copolymers for adhesive use are ethylene vinyl acetates (EVA)
those containing 25-40% by weight of vinyl acetate. A high VA content in the
copolymer leads to greater solubility, high tack in the adhesives, better adhesion to
polar surfaces and better low temperature perfomiance. EVA hot melt adhesives
are used in bookbinding and pressure sensitive adhesives.

2. Polyamides (nylons)

Polyamides are employed as single component hot melts. A number of hot

melt polyamides are produced by copolymerisation of multiple diacids or
diamines. Polyamide hot melt adhesives are used in packaging textiles and in
furniture, shoe and electronic industries. Excellent adhesion to plasticized PVC,
porous materials and metals are reported for polyamides.

3. Poly (vinyl acetate)

PVAc is almost always used in emulsion fomi. The largest adhesive

application ofPVAc is in bonding paper. PVAc adhesives are used in bookbinding,
bag seaming, tube winding, cup adhesives, remoistenable adhesives on stamps and
envelopes, and for bonding various films to cellulosic materials. Polyvinyl alcohol
derived from PVAc is used as a component of PVAc emulsions.

4. Poly (vinyl acetal)

Two commercial resinsof this type of materials, poly (vinyl formal) and
poly (vinyl butyral) are produced by the reaction of poly (vinyl alcohol) with
formaldehyde and n-butyraldehyde respectively. They are used in structural
bonding, primarily of metals, and for the manufacture of automotive safety glass.
Poly (vinyl butyral) combined with plasticizers, extending resins and waxes are
used as interlayer in laminated automobile safety glass. It cunently dominates this
area internationally.
 Introduction

5. Acrylics

Acrylic adhesives are derived from acrylate or methacrylate esters. An

important industrial application of acrylic emulsions is in bonding nonwoven
fabrics. Acrylates are used very widely in pressure sensitive adhesives. The
principal constituents of these adhesives are either butyl or octyl aciylate, along
with polar monomers such as acrylic acid or acrylamide.

Advantages of acrylic adhesives are tolerance for oily and otherwise poorly
prepared surfaces, rapid bonding at room temperature, low shrinkage during cure,
high peel and impact strength combined with excellent shear strength, good
environmental resistance and elevated temperature properties (I52).

e. Adhesive alloys

These are made by combining resins of two different chemical nature chosen
from the thermosetting, thermoplastic or elastomeric classes. The thennosetting
resin, chosen for high strength, is plasticized by the second resin, making the alloy
tougher, more flexible and more resistant to impact. The adhesive utilizes the most
important properties of each component material. They are commonly available as
solvent solutions and as supported and unsupponed films.

Adhesive alloys used include epoxy — phenolic, epoxy — polysulphide,

epoxy — nylon, nitrile - phenolic, neoprene — phenolic, vinyl —- phenolic, polyvinyl
acetal ~ phenolic etc.

1.2.2 Neoprene adhesives

Polymer structure of neoprene is (lBi8I'I11ll1€Cl by the manner in which the

monomer 2 chloro-1, 3- butadiene reacts with the growing polymer chain. Upon
pOlymerisation, chloroprene may take any of four isomeric forms shown in
Fig.l.l6
H

Cl Cl H I

_C|'|2 —?-:C-C}-|2— —CH2—(I§:(Ij__CH2_

Trans 1, 4 addition Cis 1,4 addition
ghapter I _ _
""CH2'“"‘*
c
9
l - Cl
"" __CH2__ —'

1, 2 addition 3,4 addition

Fig. 1.16 Structure of neoprene

The proportions of these configurations in the polymer determine the amount

of crystallization (trans I, 4) and reactivity towards vulcanization (1, 2 addition).
Rapid bond strength development of neoprene adhesives is associated with
crystallization of trans configuration in which there is no side group bulkier than
chlorine atom.

Different grades of neoprene are

Neoprene AC: General purpose, quick setting adhesive elastomer containing about
90% trans 1,4. It has good stability and cohesive strength
Neoprene AD: Similar to AC with better colour and viscosity stability.
Neoprene AF: Carboxylated, slow crystallizing rubber, develops cohesive strength
rapidly and has excellent resistance at elevated temperatures.
Neoprene HC: The most rapidly crystallizing type and hence suitable for cold
setting, heat sealable adhesives.
Neoprene FB and F C: Slow crystallizing, high viscosity fluid elastomer.
Neoprene AT: Highly reactive peptizable polymer that can be used as a base for
pressure sensitive adhesives requiring high peel strength and flame resistance.
Neoprene AG: High gel polymer, provides improved application properties.
Neoprene A11: Dispersable, non ctystallizing, chemically peptizable polymer.
Neoprene W: General purpose elastomer, non crystallizing, contains 85% trans 1,4
segments, good tack and low cohesive strength.

Neoprene adhesives are used as elastomeric binders because of high bond

strength, bonding range, high ultimate strength and creep resistance, adhesion to
 _ I utroducti on

many surfaces, durability, flexibility, chemical resistance and resistance to buming.

Strength of neoprene is associated with crystallization as the polymer is deposited
from solution (I53). Rapid bond strength development of neoprene contact adhesives
is associated with crystallization resulting from high level of trans configuration in
which there are no side groups bulkier than chlorine atom. The temperature and
solvent resistance can be considerably increased by additional crosslinking with
phenolic resins which also improves tack and adhesion. Thennal resistance is
enhanced further by addition of bivalent oxides of the second main group and
subgroup metals such as calcium and zinc. By increasing the amount of resin the heat
resistance is raised, the elongation reduced and therefore brittleness of the adhesive
layer enhanced. A 40-45% resin level seens to be the best compromise.

CR types with medium or strong crystallization tendency are preferred. CR

is soluble in aromatic chlorinated hydrocarbons, in some esters, ketones and also in
mixtures of certain non-solvents. The nature of the phenolic resin used influences
the open time and peel strength to a great extent. The content of methyl groups and
dimethylene ether bridges are the key factors which have to be coordinated with
the crystallization tendency of CR. If the crystallization rate is high non-or less
basic reactive phenols is of advantage (I54).

A typical neoprene contact adhesive contains 100 parts neoprene, 45 parts t­

butyl phenolic resin, 5 parts M gO, 2 parts ZnO and an antioxidant. Phenolic resin
first reacts with MgO in the presence of water resulting in a three dimensional
system. MgO also functions as an acid acceptor. Neoprene contact cements have
important uses in shoe industry, automotive and construction industry.

1.2.3 Phenolic adhesives

Phenolics are condensation products of phenol and fomialdehyde. A large

variety of phenolic resins are possible depending on (I) choice of phenol. (2) P: F
ratio (3) type and amount of catalyst used (4) time and temperature of reaction.

Phenolic adhesives employed are provided either as one component, heat

curable liquid solutions or powder, or as liquid solutions to which catalysts must be
\
added. In general phenolic resin exhibits adhesive functions in all kinds ot
applications. Their adhesion to most materials is very good due to the marked
Chapter I _
polarity of the phenolic structure. Disadvantages are their brittleness, the high
curing temperature and pressure required and the limited shelf life of resol grades.

In structural adhesives, the phenolic resin for metal /metal and metal /rubber
bonding are combined with elastomers or thermoplastics. By these combinations the
characteristic properties of both can be utilized and specific requirements met by the
ratio of resin and elastomer. As soft components polyvinyl acetate, NBR, polyamides
and polyaeiylates are preferred. The elongation, elasticity and resilience of the
phenolic resin is improved considerably especially at low temperature by this
binding. The toughening action of such polymer blends is attributed to chemical
reaction and the morphology of the cured system. Because of the limited solubility of
the thermoplastic or elastomeric component a discrete, discontinuous phase develops
in the cured phenolic matrix- Crack propagation is considerably minimized by the
two-phase system and the impact strength therefore improved.

Adhesives based on neoprene and NBR exhibit high green strength and
excellent adhesion to various substrates. The strength, temperature and creep
resistance can be improved and adhesive cost reduced by the addition of phenolic
resins. Chloroprene adhesives yield high peel strength and have outstanding green
strength properties. Nitrile adhesives exhibit excellent oil and grease resistance.

An important use of phenolic adhesives is in wood bonding where water

resistance is required. Phenolics may be formulated as water dispersions, where
penetration into the cell structure of wood is important for the formation of
permanent bonds. Resorcinohformaldehyde condensates are also used as wood
adhesives. Resorcinol resins cure at room temperature under mildly alkaline
conditions and are therefore used for wood bonding applications.

Unmodified phenolies are mainly used as primers, to prepare metal surfaces

for bonding and as binders for such varied products as glass wool insulation mats,
foundry sand, abrasive wheels and brakelining composites. Phenolic resins are also
used in the manufacture of abrasive devices such as grinding wheels and sand
papers. Laminates of various fabrics are prepared by impregnating the sheets with
phenolic resin (155).
 _ Introduction
Other phenols used are cresol, p-nonyl phenol, p-phenyl phenol, p-tertiary
butyl phenol, p-amyl phenol and p-oetyl phenol. Phenols substituted at either the
ortho or para positions are only difunctional, hence the resins are incapable of
crosslinking to a usefiil thennoset structure. The meta substituted isomer is
trifunctional and therefore crosslinking will occur.

1.2.4 CNSL based adhesives

The high polarity and inherent tackiness of phenolic materials and the ease
with which liquid to solid conversion can be accomplished make CNSL a desirable
starting material for adhesive formulations (156).

There are many reports and patents describing the use of CNSL polymers in
adhesives. In these formulations resins derived from CNSL by various polymerisation
and/or modification techniques are employed. Details are given in (I57).

CNSL based adhesives exhibit admirable properties to meet the growing

demand for quality and durability in bonding plywood. Low grade wood
impregnated with CNSL resin shows remarkable upgrading of quality. These resins
are used for the preparation of partieleboards, bamboo boards, coconut leaf based
boards etc. where both quality and cost effectiveness could be simultaneously
achieved.

Polymerisation of CNSL with HZSO4 as the catalyst followed by

compounding with aldehyde type hardeners leads to cold setting adhesives (158).
Polymerized CNSL obtained using HCI, HNO3, MnO;, maleic acid or stearic acid
as catalyst was found to be a good plywood adhesive (l58). Alkali catalyzed
CNSL-phenol- formaldehyde condensates compounded with CuCl2 or CaCO3 are
excellent adhesives for plywood (I60). Cold setting adhesives meeting Indian
Standards specifications have been prepared from alkali catalyzed CNSL- phenol­
formaldehyde resin and p- toluene sulphonie acid (161). Cure time of adhesives
obtained from CNSL, phenol and formaldehyde was reduced when Kl\/InO4 was
used as accelerator (I62). CNSL modified phenol- formaldehyde resins have been
reported as useful adhesives for heat bonding metals to polymers (163). Heat
curable adhesives have been prepared using a formulation consisting of CNSL
resin and epoxy resin (164). Polymerisation of CNSL mixed with
Chapter I

paraformaldehyde has been used as cements for corrosion resistant tanks (165). An
increase in self adhesion strength with storage time was observed for PCNSL
modified NR (166)

In this study, adhesives consisting of resins derived from CNSL and

neoprene rubber have been investigated for rubber- to- rubber, rubber-to- metal and
metal- to- metal bonding.

1.3 AGE RESISTORS FROM CNSL

The incorporation of CNSL has been found to improve the properties of

rubber products. It aids processing and enhances the vulcanization properties (68).
It also helps the incorporation of ingredients into rubber, increases its resistance to
moisture, resistance to crack and cut and thermal stability.

1.3.1 Mechanism of ageing

The ageing of polymers occurs through a free radical process. Any form of
energy — heat, light or mechanical stress can break polymer bonds to form carbon
radicals (C) to start the degradation process. ln the presence of oxygen, peroxy
radicals (C OO.) are formed. The peroxy radical abstracts hydrogen from the
polymer to generate another carbon radical and a hydroperoxide (COOH). The
hydroperoxide decomposes under heat to form two or more free radicals, an alkoxy
radical (CO ') and a hydroxyl radical (HO '). Each ofthese radicals can abstract a
hydrogen atom from the polymer backbone to form yet more carbon radicals. Each
time additional free radicals are generated. Two free radicals can combine to
terminate each other, which results in new crosslinks. Polymers with many double
bonds provide many attachment sites for polymer radicals, leading to many
crosslinks. These polymers become stiff and brittle consequently.

Other polymers undergo reversion or chain scission during ageing. Scission

is favoured in polymers that are branched or have many side groups. During ageing
alkoxy or carbon radicals are generated which undergo beta scission or
unimolecular cleavage to lower molecular weights. These polymers degrade by
becoming soft and tacky.
 Introduction

The exposure of rubber products to elevated temperature during the service

life will result in gradual degradation of the product so that ultimately it may no
longer fulfill its function. The rate at which this degradation takes place will be
greatly accelerated under aerobic conditions, heat acting as catalyst for the
oxidation process (167).

Various ageing processes are

a. Oxidative ageing —- Oxidation of rubber vulcanizates is technologically
important since the absorption of only a small amount of oxygen (1%) by
rubber vulcanizates results in considerable change in physical properties.
Natural and synthetic rubbers are attacked by oxygen and the reaction is
accelerated by heat, light and the presence oi‘ certain metallic impurities which
catalyze the decomposition of peroxides to fonn free radicals.
b. Accelerated oxidation in the presence of heavy metal compounds

Many heavy metal compounds, like copper and manganese have a catalytic
action on the oxidation of rubber vulcanizates. Even traces of (0.001 wt %) copper
and manganese compounds are able to accelerate the oxidation of rubber
vulcanizates

c. Heat ageing in the absence of oxygen

Various reactions can take place in the absence of oxygen- thermal

decomposition of crosslinks, continuation of inter or intramolecular network or
shifting of crosslinks without change in the total numbers

d. Fatigue

When rubber is subjected to prolonged mechanical stress changes, cracks

will slowly develop in the material and they grow until they lead to complete
breakage of the article. lligher temperature and higher frequency of stress change
accelerate crack formation.

e. Ozone crack formation

When vulcanizates are exposed to weather conditions in a static extended

mode, cracks appear perpendicular to the direction of the applied stress. Small
amounts of ozone in the atmosphere are the cause. Without extension of the
Chapter I

vulcanizates cracks are not formed. A critical extension has to be exceeded in any
case before cracks show up. With increasing extension, the number of cracks
formed per unit area and time increases rapidly. The speed of ozone crack
formation depends on temperature and humidity of air. Totally saturated elastomers
are ozone resistant.

f. Crazing effect

When an unstressed vulcanizate is exposed to weather, especially prolonged

sunlight, unoriented cracks can develop on the surface. The surface can, after
prolonged irradiation become brittle.
g. Frosting phenomena

Frosting is caused by the action of warm, moist, ozone containing

atmosphere on vulcanizates.

1.3.2 Phenolic age resistors

Age resistors react with the agents oxygen, ozone, light, weather and
radiation which are responsible for the deterioration process. This in turn prevents
or slows the polymer breakdown, improves the ageing qualities and extends the
service life ofthe product involved (168).

Phenolic resin can give thermally stable crosslinks. The service life of
sulphur cured vulcanizates can be improved by using PF resins. In the case of
certain rubbers like IIR, NBR and SBR phenolic resin leads to crosslinking of the
rubber and this improves the ageing behaviour. CNSL based resins are prospective
candidates for this modifying action on rubbers. Retention of tensile modulus,
tensile strength and elongation at break of natural rubber vulcanizatcs containing
phosphorylated CNSL (PCNSL), 2-ethyl hexyl diphenyl phosphate and aromatic
oil after ageing has been investigated (169,170). The vulcanizates containing
PCNSL showed good retention of tensile properties after ageing due to the post ­
curing reactions during the ageing period (171). The effect of addition of paraffin
oil, vegetable oil, castor oil and CNSL to natural rubber compounds has been
compared in tenns of the mechanical properties (I72). Polymerized CNSL has
been recommended as a substitute for DOP, DBP for nitrile rubber and neoprene
rubbers (I73). CNSL- phenol- formaldehyde resin when incorporated into rubber
 W _ I nfroduction

articles improves resistance towards cracking and action of ozone (174). Sulphur
vulcanized NR containing CNSL possesses greater resistance towards oxidation\
(175). The formation of a network bound antioxidant (78) or the formation of
phenolic sulfides in situ during the vulcanization (79) have been used to explain the
antioxidant acitivity of CNSL derivatives in natural rubber vulcanizates. The steric
effect due to long tail substituents, has been also reportes as an important factor
(50). The alkyl substituents could trap both alkyl and peroxy radicals and increase
antioxidant acitivity (80). CNSL condensed with formaldehyde has been
recommended as an effective antioxidant for SBR (176). Cardanol is used s
vulcanizing agent for IIR (I77). Modification of NR with i0-15 phr of PCNSL.
resulted in improvement in tensile properties along with a lower degree of stress
relaxation at high shear ratios and strain levels (178). Bromo derivatives of PCNSL
improved the flame retaedant characteristics of NR vulcanizates (179 ).Rheological
studies on blends of NR and PCNSL indicates the plasticizing effect of PCNSL and
good compatibility between NR and PCNSL (180 ). PCNSL lower the activation
energy of vulcanization of NR (181).

ln this study, CNSL is used in the resin form as well as naturally occurring
oil for modifying the ageing properties of various elastomers.
1.3.3 Other age resistors
a. Antioxidants

Antioxidants are substances that retard oxidation by atmospheric oxygen at

moderate temperatures. Oxidation by atmospheric oxygen is a free radical chain
reaction and can be inhibited at initiation and propagation steps.

All commercial important antioxidants fall into four classes (182) ~- amines,
phenols, metal salt of dithioacids and bound antioxidants.
1. Amine antioxidants are strong protective agents but discolour and stain to
various degrees. Examples are diphenylamine, naphthylamine, alkyldiamine,
quinoline, phenylenediamine etc.
Z. Phenol is less discolouring than amines. Most of the commercial antioxidants
are of this type. eg. styrenated phenol, 2,2,4 — trimethyl- l ,2-dihydroquinoline.
ln high temperature applications, polynuclear phenols generally are preferred
over monophenols because of their lower sublimation rates.
Chapter I g w
3. Metal salts of dithioacids act as hydroperoxide decomposers and propagation
inhibitors and are used in conjunction with other antioxidants, particularly
phenols for rubber, petroleum products and plastics.
4. Bound antioxidants are copolymerized into the elastomer chain. The main
advantage of such a system is low antioxidant extractability in applications
where the elastomer is in contact with solvents capable of extracting
conventional antioxidants.

According to their mode of action antioxidants are classified as primary or chain

breaking and secondary or preventive antioxidants
v

I. Chain breaking antioxidants interfere with the chain propagation steps oi

polymer degradation. These antioxidants terminate the chain by
i. Free radical traps which interact with chain propagating R02.
radicals to form inactive products. Quinones and conjugated
molecules can function as free radical traps.
ii. Electron donors give electron to peroxy radical thus stabilizing the
system
iii. Hydrogen donors are the most commonly used chain terminating antioxidants.
inhibitors of aromatic amine type interfere with oxidative chain propagation by
competing with the polymer for peroxy radicals.

2. Preventive antioxidants
i. Light absorbers: Ageing induced by light can be prevented by using
photostabilizers like hydrobenzophenone derivatives, benzotriazole
derivatives, metal complexes of different metals etc.
ii. Metal deactivators: These are strong metal ion complexing agents that
inhibit catalyzed initiation. eg. Ethylene diamine tetra acetic acid.
iii. Peroxide decomposersz These reduce hydroperoxides to alcohols without
substantial formation of free radicals. eg. zinc dialkyl dithiophosphates.

Most conventional antioxidants trap the peroxy radicals or decompose the

hydroperoxide. Amines and phenols are radical traps for peroxy and alkoxy
radicals. Phosphites are peroxide decomposing antioxidants.
 I n troduc Q it

b. Antiozonants

Atmospheric ozone degrades polydiene rubbers by reacting directly with

polymer main unsaturation. The most effective compound for ozone protection
under static and dynamic stress are nitrogen substituted p-phenylenediamines. They
increase the critical energy necessary to form ozone cracks. Therefore crack
formation will start at higher extension and crack growth rate will be reduced.

c. Ageing protection against hydrolysis

Elastomers containing hydrolysable groups in the rubber matrix or in the

side chain can be degraded by moisture. Ageing protectors for such rubbers should
react with steam and moisture faster than rubber eg. carboimides

d. Ageing protectors against crazing

Ageing protectors used against crazing are alkylated phenols. The quantities
used lie between 0.5 — 2 phr.
e. Ageing protectors against frosting

The best protection against frosting is obtained by proper choice of fillers

and vulcanization accelerators. To some extent p, p’ diaminedipheny] methane acts
against frosting.
f. Ageing protectors against fatigue

The most effective fatigue protectors are aryl/alkyl-substituted p­

phenylenediamines

g. Ageing protectors against rubber poison

The protection of rubber vulcanizates against Cu and Mn depends on a

complex formation of the damaging ion. Ethylene diamine tetraacetic acid can act
as copper protector.

h. Ageing protectors against heat ageing

For the selection of ageing protectors for heat resistant vulcanizates their
volatility is important. The volatility depends strongly on the molecular structure.
The least volatile protective agent yields the highest high temperature resistance.
Chapter I _

1.4 POLYMER WOOD COMPOSITES FROM CNSL.

Composite wood products may be produced using wood fibers, flakes, chips
or shavings or veneers. During the manufacturing process these materials are often
combined with different glues, resins, water repellents and preservatives to produce
sheet boards. Addition of CNSL increases the heat resistance of phenolic molding
compositions (183). Major composite wood products include (1) particleboard
(from wood flakes, shavings or splinters) (2) fiberboard (from fibers of wood) (3)
plywood (from one or more veneers) (184).

Acid catalyzed CNSL —formaldehyde resins cured with CuCl; have been
used as adhesives in the manufacture of particleboard (185). Alkali catalyzed
CNSL- formaldehyde resins have been recommended as bonding materials for the
preparation of particleboard (186). Composite panel showing excellent ablation
characteristics were developed from CNSL (187). Properties of particleboards from
hemp fibre and CNSL (I88) and coffee husk and CNSL (18.9) have been reported.
Particleboard were prepared from rice husk by mixing them with resin prepared by
the condensation of CNSL with formalehyde and an alkaline catalyst (190).
Medium density fiberboards have been moulded comprising coir fibree, CNSL and
formaldehyde (191, 192). Jute reinforced composite laminate have been
manufactured by soaking jute in a CNSL- modified formaldehyde phenol
eopolymer and pressing together several layers of the soaked jute (193). Fire
resistant coconut pith sheets for use as building materials have been prepared by
mixing coconut pith and adhesives prepared by copolyrnerising CNSL with
orthophosphoric acid and neutralizing the polymer before mixing it with
formaldehyde and HMTA (194). Mechanical and thermal properties of boards
made with kenaf fibers and CNSL have been investigated (195). Central Building
Research Institute (CBRI), Roorke, lndia has developed medium density composite
doors containing coir fiber, CNSL and parafonnaldehyde (196). A novel resin has
been developed by the Centre for Advanced and Renewable Materials, Bangor,
Wales based on CNSL primarily for use in particleboard (197)
 __ Introduction

1.4.1 Particleboard

Wood waste of the wood working industry induced the idea of

particleboards. The story of the growth of the particleboard industry may be found
in the review article by Klauditz (198). Particleboards are made from almost any
form of wood residue except bark.
a. Wood fillers - dzfferentforms
I. Cut flakes -- These are prepared by slicing wood into flat thin particles in
which the grain direction of wood lies in the plane of the particle. With this
type of particles high length to thickness ratio can be developed. Such
particles orient very well in the plane of the board, so that maximum bending
strength and dimensional stability can be achieved.
2. Planar shavings- Planar shavings tend to have undesirably high bulk because
of their curled nature, and to reduce their bulk, the shavings may be passed
through a mechanical reduction treatment to split them and eliminate curl.
Compared to flakes, shavings have a lower net length to thickness ratio.
Planar shaving boards tend to develop higher strength in the direction
perpendicular to the plane of the board. A detailed study of the use of planar
shavings in particleboard has been made by Heebink et al. (199).
3. Splinter — Splinter is produced from solid wood residue by human milling.
Splinter is produced without any cutting action. Instead the wood is broken
down by a hammering or smashing action. This breakdown process tends to
produce comparatively blunt particles in which length to thickness ratio of the
particles is still less favorable than is obtained from pure planar shavings. The
actual shape of the particle depends on the species used and moisture content
(200)
4. Sawdust — Sawdust represents a still lower grade of wood residue. The work
by Klauditz and Buro (201) explores the use of sawdust in particleboard as a
mixture with high quality flakes.
5. Bark and sander dust — These materials are wood residues of the lowest
value. Bark does not have the oriented fiber structure of wood and therefore
has low strength. Sander dust appears as a residue from a plywood operation.
and in greater quantities from a particleboard mill.
b. Ingredients of particleboard
I. Adhesives
i. Thermoset binders— Commonly used thermoset adhesives include phenol
formaldehyde, urea fomialdehyde and melamine formaldehyde.
a) Phenol formaldehyde — PF is available as powdered resin and as liquid resin.
Liquid resin is a water dilutable aqueous resin containing small amounts of
caustic soda. Powdered phenolic resin has one particular process advantage in
boards made from flakes. These long flakes do not fluidize readily. Powdered
resin mechanically mixed with the flakes tends to distribute uniformly over
the particles. The performance of the synthetic resins as particleboard binders
has been studied by Carroll (202). The efficiency of these resins depends on
the proportion of the resin binder and the moisture content of the wood.
Excess moisture content tends to plasticize the resin and can also retard the
cure of the resin. CNSL based resin can be used in the present context as the
adhesive.

b) Urea formaldehyde — The major virtues of UF resin are low cost, rapid cure,
process convenience and clear colour. The resin is commonly supplied in the
form of an aqueous resin solution containing 60-65% solids and with viscosity
in the range of 200-500 cp. It is also available in powdered fomi which can be
reconstituted to an aqueous solution, a form that is more suitable for shipment
to isolated board plants.

Two main objections to UF resin now used are its tendency to release
formaldehyde fumes when the finished board is exposed to heat and humidity
and the lack of complete durability of the resin especially towards moisture
(203). If the durability of the particleboard is inadequate for an intended
application UF resin may be modified by addition of resorcinol-formaldehyde
or MF resin
c) Melamine formaldehyde — MF resins are used primarily for decorative
laminates, paper treating and paper coating. They are more expensive than PF
resins. MF resins may be blended with UF resins for certain applications.
 Introduction

ii. Proteinaceous and thermoplastic binders

Other binders used in particleboard manufacture are proteinaceous adhesives

and thermoplastic adhesives. Proteinaceous adhesives have high inherent viscosity
which is unsuited for spray application and their water resistance is generally poor.
cg. Soybean glue, caseine glue.

Inorganic binders used are portland cement, magnesite cement and gypsum.
The finished product is low in bending strength, high in compressive strength and
is resistant to fire and insect attack.

2. Additives

Particleboard retains many of the properties of wood from which it is made.

For most applications, the properties of these boards are adequate. For special
applications, the properties of the boards may be modified by the addition of
chemical agents to provide additional properties such as water repellence, fire
resistance and resistance to decay or insect attack.

i. Paraffin wax — Paraffin wax imparts water repellency to board (204).

The amount of wax used is 1-1.5% referred to dried wood. A higher
percentage reduces binder wetting and adhesive strength (205).

ii. Fungicides and insecticides — For a few applications of particleboard,

wood does not have sufficient resistance to attack by filngi and
insects. Resistance to fungi can be improved by the addition of
pentachlorophenol in amounts not more than I-2% of the wood (206).
Tri butyl tin oxide or fluorine compounds in quantities up to 1.5% are
also used (207).

iii. Flame retardants - The requirements of flame retardance can be met

by adding flame retardant materials. Ammonium hydrogen phosphate
and ammonium polyphosphate are preferred. They may be used in
combination with halogen compounds. The addition of inorganic
substance like vermiculate or perlite has been recommended but
board strength is reduced.
Chapter 1? A _ fié
c. Properties and uses of particleboard
Table 1.7 shows the requirements for different grades of particleboard as
specified by American National Standards for particleboard ANSI A208 1 (NPA
1993)(20s).

Table 1.7
Particleboard grade requirements
Grade’ llntenialbond iMOR 5 M019. I
H-1
q (MPa) A (MP21) (MPa
1 0.9 16.5
l) 2400
—i1

H-2 0.9 20.5 2400

H-3
M-1 0.4 1 23.5
11
2750
1725
M-S 1’ 0.4 12.5 1900
M-2 0.45 14.5 2225
M-3 0.55 16.5 2750
LD-1 0.1 3 550
LD-2 0.15
11 . 1
5 1025

H= density > 200 kg/m3, M=density 640 to 800 kg/m3, LD= density <040 kg/m
M-S refers to medium density; special grade added to standard grades M l M 2
and M-3. Grade M-S falls between M-1 and M-2 in physical properties.

Table 1.8 shows the requirements for different grades of particleboard as per
IS 3087-1985
 Introduction

Table 1.8
Physical and mechanical properties of flat pressed single
layer particleboard (IS 3087-1985)
P Properties if 0 PM 8 M
"Density 0 P 8 0 solo-900 Kg/m3
Moisture content ‘ 5- 15°/1
Water absorption t 50%
MOR ll N/mmz \
(24h soaking)

Tensile strength (perpendicular to surface) F ‘

(Up to 20 mm thickness) 0.8 N/mmz
Particleboard is used for fumiture cores and as underlayment.

1.4.2 Plywood
hi general, plywood is a material made of at least three layers of wood,
mostly veneers, with application of adhesives, pressure and heat (209). Plywood is
generally classified into interior and exterior grades.
Exterior type plywood will retain its glue bond when repeatedly wetted and
dried or otherwise subjected to weather and is intended for permanent exposure.
Within each type there are a number of panel grades based on the quality of
veneers and the panel construction.

a. Ingredients of plywood
Non modified resols catalyzed by NaOH are used for weather resistant
plywood. In order to adjust wetting and avoid excessive penetration and to obtain a
uniform joint thickness, diluents and fillers are almost always used. Rye or wheat
flour can be used for interior grades and non-swelling fillers like coconut shell
flour for exterior grades. Apart from cost reduction the brittleness of the adhesive
joint is reduced by these additives.

b. Properties and uses of plywood

Plywood has high strength- to- weight ratio and strength — to-thickness ratios. lt
has excellent dimensional stability along its length and across its width and minimal
Chapter I g

edge swelling. Plywoods are used as roof sheathing, subfiooring and numerous
applications in panelling and furniture apart from countlesss industrial applications.
1.4.3 Fiberboard
Fiberboard includes hardboard, medium density fiberboard and insulation
board. Because wood is fibrous by nature, fiberboard exploits the inherent strength
of wood to a greater extent than does particleboard. To make fibers, bonds between
the wood fibers must be broken by attrition milling. This can be accelerated by
water soaking, steam heating or chemical treatments. A number of classifications
of fiberboards can be given according to the appearance, method of production,
kind of application and specific gravity (210)

a. Ingredients of fiberboard
Only wood of inferior quality and industrial wood is used for the production
of fibers. The bark is not completely removed because its presence up to l5% does
not affect the properties of fiberboard substantially. Sawdust can also be added
upto 30%. ln general, fiberboards can be produced without bonding agents, using
only the bonding ability of the fiber. ln order to improve mechanical properties and
to reduce -water absorption and swelling, phenolic resins are used as bonding
agents. Urea resins are also used. Urea resins are used for boards which are not
subjected to high humidity.

Dry resin content for boards is l-3% calculated on dry fiber weight. The PF
resin is precipitated out of a diluted aqueous solution by acidic chemicals like
diluted sulphuric acid or aluminium sulphate and fixed to the fiber. Hydrophobic
\
agents like wax and paraffin reduce water absorption and swelling. The amount ol
wax is normally within the range of 1% based on the weight of the dry fiber.
Furthermore, flame retardants, fungicides and insecticides, release agents and other
improving materials like drying oils can be added.

b. Properties and uses of fiberboard

The most familiar application is acoustical tile. In building construction,
\
insulation board panels find use as boards for poured- in- place concrete, rigid roof
insulation for built up roofs, and low cost single backing.
Medium density panels have found acceptance as siding. Sound transmission
from one room to another is reduced through the use of insulation board pmdu¢1S_
 Introduction

Medium density board is used in place of solid wood in many furniture

appHcafions(2ll)
Hardboard is widely used in building construction for paneling, siding,
decking and in manufactured products such as garage doors. In automobiles it has
been used for door panels, for a package shelf, and for interior roof linings
1.5. CNSL BASED PHENOLIC RESIN

By virtue of its phenolic nature CNSL can be condensed with formaldehyde

to give PF type resins. Phenolic resin discussed in the earlier section can be
prepared starting from CNSL by similar methods. Reactions of CNSL are
discussed in Section 1.1.5 and preparation of CNSL based resins in Section 2.3.
The long chains in CNSL impart flexibility due to intemal plasticizing, resulting in
the fonnation of soft resins at elevated temperature unlike phenol- formaldehyde
resins which are hard (212).

1.6 SCOPE AND OBJECTIVES OF THE WORK

CNSL can be polymerized in a variety of ways: addition polymerisation

through the side chain double bonds, condensation polymerisation through the
phenolic ring, oxidation polymerisation etc. Several modifications are possible due
to its special structural features. CNSL is cheap, renewable and underutilized. It
can replace phenol in many applications. Greater utilization of CNSL as a
monomer for industrial polymer products can be an attractive proposal in view of
its low cost, abundant availability and chemically reactive nature. By using CNSL
in place of phenol, phenol derived from petrochemicals can be conserved and a
cheap agro-byproduct can be utilized.

The overall objective of the study is to develop new applications for CNSL
in the polymer field.

Specific objectives of the work can be stated as follows

1. To synthesize CNSL-phenol-hexa resin and study the etitect of varying

parameters phenol: formaldehyde and CNSL: phenol ratios on the properties
of the synthesized resin.
Chapter 1? __ _ _ **** _A
2. To study the adhesive properties of blends of neoprene and CNSL based
resin for bonding metal-to-metal, metal- to- rubber and rubber- to- rubber.

3. To study the effect of synthesized CNSL based resin as age resistor for the
elastomers NBR, SBR, CR, HR, EPDM and NR.

4. To develop particleboard from wood waste and CNSL based resin

 Introduction

REFERENCES
1, M.T. Harvey and C. Caplan, 1nd.Eng.Chem., 32 (I0), I306 (I940)
2. S.ManjuIa, J.D.Sudha, S.C.Bera and C.K.S.PilIai, J.AppI.PoIym.Sci.,
30,1767 (I985)
3. Economic Review (2004).
4. G.Stadeler, Ann. Chem. Pharm., 63,I37-I64 (I847)
5, A.R.R. Menon, C.K.S. Pillai, J.D.Sudha and A.G.Malhew, ].Sci.Ind.Res., 44,
324 (I985)
6, P.H.Gedam and P.S.Sampathkumaran, Pr0g.Org.Coat., I4, I 15 (I986)
7. J.H.P.Tyman, Chem.Soc.Rev., 8, 499-537 (I973)
8. J .H.P.Tyman, D.Wielezynski and M.A.Kashani, J .Am.Chcm.Soc., 55, 663 (I978)
9. P.A. Mahanwar and D.Kale, Indian J. Techn0I., 3, I91-193 (I996)
I0. V.Paul and L.M.Yeddanapally, Nature, I74, 604 (I954)
ll. W.F.Symes and C.R.Dawson, Nature, 171,841 (I953)
I2. J.A. Cornelius, Trop.Sci., 8(2), 79 (I966)
I3. Indian patent 78612, Sep 25 (I96I).
14. S. Siddiqui and A.A. Khan, Indian Patent 32237 (I945)
I5. J.H.P.Tyman, .I.Am.Oil.Chem.Soc., 66 (4), 533-537 (I989)
I6. R.L.Smith Jr, R.M.MalaIuan, W.B. Sctianto, II.ln0maIa and K.Arai,
Bioresource Technology, 88, I-7 (2003)
17. R.K.Jain and K.Sivala, .I.Fo0d Engg., 32 (2), 339-345 (I997)
18. M.T.Harvey and S. Caplan, Indusrial and Engineering Chemistry, 33, I0,
1306-13100940).
19. L.C.Anand, J.-Petro Chem., I2 (5), 3 (1981)
20. H.T. Han/ey, U.S Patent 2434797 (I948)
21. V. Madusudhan, M.Sundaramaiah and N.B.Naidu, Indian .I.'I‘ccli., I I, 347 (I973)
22. H.Barron, Use of CNSI. resin in modern plastics, 2"“ cdn, P 84, Chapman and
Hall, London (1949)
23. R.Antony, C.K.S.Pillai and K..I. Scariah, J.Appl._Polym.Sci.,4l, I765 (I990).
24. N.R.Krishnaswamy and K.P.Govindan, Chem.Ind., I892 (I958)
Chapter 1 _ ,4 ,_
25. I.N.Hema1etha, H.Dakshinamurthy and S. Agganval, Paint Manuta, 39 (1 1),
41 (1969)
26. D.S.Basu and A.K.Kar Che-m.Age India, 24 (6), 341 (1973)
27. M.K. Misra and G.N.Pandey, J.App1. Poymer Sci., 30, 969-977 (1985)
28. D.O' Conner and F.D Blum, J.App1.Po1ym.Sci., 33, 1933-1941 (1987)
29. K.Sathia1ekshmi, Bull. Materi. Sci.,16, 137 (1993)
30. S.Le11ka, A.P.Das and P.L.Nayak, J .Po1ym.Sci.Po1ymer Chem., 30,4619 (1985)
31. J.S.Aggarwa1, Paint manuf., 36, 29 (1966)
32. M.T.Mortimer, Cashew News, 1 1,16 (1977)
33. K.K.A1va, Shridara, J.Macrom01.Sci., A 34(4), 665-674 (1997)
34. S.Cap1an US Patent 216059 (1940)
35. M.T.Harvey, U.S. patent 2324300 (1943)
36. Harvel Corporation Bp 627927 (1949)
37. C.R. Dawson and D. Wasserman, US Patent, 2502436 (1950)
38. C.R. Dawson and D- Wassemian, US Patent, 2502708 (1950)
39. Harvel Corporation BP 625497 (1949)
40. S. Captain and D.E. Rosamila U.S. patent 2476692 (1949)
41. H.F. Haufman and J. Een/e. Fette. Sieten Anstridu 69(8), 577-582 (1967).
42. H.M. Shivadasami BP 1279257 (19720
43. Y.K. Kamath, S.V. Puntunibekkar and D.B. Vidwans, Paintindia, 14, 4, 21 ( 1964).
44. A.R.R.Men0n, C.K.S.Pi11ai and G.B.1\1ando, .1.Adhes.Sci.Tech., 9, 443-451
(1995)
45. /\.R.R. Menon, Rubber Rep. 15 (4), 149 (1990)
46. A.R.R.Menon, C.K.S.Pi11ai and G.B.Nando, Kauts. Gummi. Kunsts., 45 (9),
708 (1992)
47. A.R.R.Menon, C-K.S.Pi11ai and G.B.Nando, Polym. Degrad. Stab., 52(3), 265
(1996)
48. /\.R.R.Menon, C.K.S.1’i11ai and G.B.Nando, Journal of Applied Polymer
Science 51 (13), 2157 (1994)
49. C.K.S.Pi11ai , V.S. Prasad, S.C. BCF3 and A.R.R.Menon Joumal of Applied
Polymer Science 41, 2487 (1990)
 H Introduction

50 V.S. Prasad and C.K.S. Pillai, Journal of Applied Polymer Science, 27, 2631
(2006)
51 H.P. Bhunia, R.N. Jana, A. Basali, S. Lenka, G.B. Nando, J. of Polymer
Science Part A Polymer Chemistry, 36, 391-400 (1998).
52 N.D.Ghatge and U.S.Pati1, Angew.Makromo1.Chem.,l9, 83 (1971); S.S.
Mahajan, Indian J.Techno1ogy, 22(1 1), 439-40 (1984)
53 C.R.Dawson and D. Wasserman U.S. Patent 3496151 (1959)
54 Minn.Mining and Mfg. Co., BP 1043346 (1960)
55 D.A.Rahu1, Paintindia, 40(8), 59-60 (1990)
56 L.C.Anand, Paintindia, 28(6), 13-33 (1978)
57 A.Orazo, Chem.Ind., 61(10), 718-726 (1979)
58 A.Orazo, Chem.Ind., 78(6), 693-696 (19.96)
59 J.S.Aggarwa1, .l.Co1our Sci.,14(3),1-9 (1975); 15(1), 14-25 (I976)
60 S.Ramanujam, Paintindia, 10, 91-106 (1960)
61 J.S.Aggarwa1, Paintindia, 17(1), 103-112 (1967)
62 A.E.Oats, lnd.Chem., 323 (1965)
63 M.Sundaramaiah, F ette Seifen Anstriokn 78, 472 (1976)
64 S.P.Potnis and J.S.Aggarwa1, J.Co1our Sci., 13 (1), 10-12 (1974)
65 N.D.Ghatge and N.N. Ma1dar,, Rubber Chem. Techno] 52 (2), 353 (1979)
66 N.D.Ghatge and B.M. Shinde, Elastomerics, 11 (12), 48 (1972)
67 N.D.Ghatge and B.M. Shinde, Rubber Chem. Techno1.. 53, 239 (1980)
68 N.D.Ghatge and R.G. Gokhale, Rubber Age, 101, 52 (1969)
69 N.D.Ghatge and R.G.Gokha1c, Indian j. Tec11., 9110), 391 (1971)
70 N.D.Ghatge and R.G.Go1<ha1e, Rubber India, 13, 2406 (1972)
71
C.R. Dawson and D. Wasserman, J.Amer.Chem.Soc., 72, 4994 (1950)
72
S.C.Selhi and B.C.S R210, Indian J.Tcc11., 2, 206 (1964)
73 M.S.Bhatnagar, Pop.P1astics, 79 (1.982)
74 D.Narayanamurthy, Res.lnd., 13(3), 134-136 (1968)
75 J.S.Aggarwa1, Paint Manuf, 43 93), 29-31 (1973)
76 L.C. Anand, Popular plastics 15-35 (1978).
_Chapter I _
77. L.C. Anand, Paintindia, 13-33 (1978)
78. R.A. Rajapakse, W.A.S. Gunasena and K.B. Wijikoon, Polymer 19, 205
(1978)
79. R.A. Rajapakse, K./Xnandakumaran, W.A.S. Gunasena and K,B. Wijekon,
Polymer 20, 887, 1979
80. F.H.A. Rodrigues, J.P.A. Feitose, N. M. P.S. Ricard0,, F.C.F. Franca and
J.P.B.. Carioca, J.Braz. Chem. Soc. 17(2),, 265-271 (2006)
81. M.T.S. Trevisan, B.Pfundstein,, R. Haubner, G.Wurfe1e, B. Spiegclhaldir, H.
Bartsch and R.W. owen, Food and Chemical Toxicology 44 (2),, 188-197
(2006)
82. Y.Koizumi,, Jpn Kokai tokkyo Koho JP 03217484 (1991)
83. http: //www.adarshsanoorcom/cnsl, January 2001
84. 1_i(t;;:_/_/wwyv.csihewindia.org/html/c0310com.ht1n downloaded on 5/3/2005
85. Jpn.K0kai Tokkyo Koho JP 0948967 (1997)
86. Jpn.Kokai Tokkyo Koho JP 09221658 (1997)
87. S. Takahata JP 09157633 (1997)
88. M.Suzuki JP 04363384 (1992)
89. Jpn.Kokai Tokkyo Koho JP 0931213 ( 1997)
90. 1-litachi Chemical C0. Ltd JP6040833 (1983)
91. Hitachi Chemical Co. Ltd JP5877934 (1982); JP 5881236 (1983)
92. M. Kikuchi, Jpn.Kokai Tokkyo Koho JP 2709136972 (1997)
93. Jpn.Kokai Tokkyo Koho JP 09286976 (1996)
94. .1pn.Kokai Tokkyo Koho JP 0948967 (1997)
95. Jpn.K0kai Tokkyo Koho JP 0849740 ( 1997)
96. K. Sakanoto and Y.Suzuki, Jpn.Kokai Tokkyo Koho JP 09132769 (1997)
97. T.Hayash, Jpn.Kol<ai Tokkyo Koho JP 0931213 (1997)
.98. H.Usui1_, M.Seko and S.l-Iiranosa Jpn.Kokai Tokkyo K0110 JP 091 1 1007
(1997)
99. F.D.B1um, J.Am.Chem.S0c, 37, A1 (1996); F.D.Blum, Po1y.Prepr., 37,733­
734 ( 1996)
100. S.C.Bera and C.K.S.Pi11ai, Indian J.Tech., 27 (8), 343-347 (1939)
 Intr0duct1'0n

101 S.Ramanujam, Paintindia, l 1 (1), 47-112 (1961)

102 A.K.G.Pi11ai 1P 158294(l983)
103 Patent No.636/DEL/96 dated 27"‘ March 1996, India
104 V.Madusudhan, B.G.K. Murthy and M.A.Sivasamban, Cashew Couserie 6(2),
12-16 (1984)
105 S.K.Swan, S.Sahoo, D.K.Mohapatra, B.K.Mishra, S.Len1<a_, P.L.Mayak,
J.App1. Polymer Sci., 1413, 54 (1994).
106 O.Akaranta, A.O. Aloko, Pigment and Resin Tech., 28(6), 336-340 (1999)
107 H.P.Bhunia, G.B.Nando,,_S.Lenka, P.L.Nayak, Eur. Polym. J., 35,1713 (1999).
108 A.R.R.Menon, A.L.Aigbodion, C.K.S.Pi11ai, N.M.Mathew, S.S.B11agawan,
Polym. J., 38, 163 (2002).
109 H.Oyabu, T.Asami, O.Yamamoto., H.Tajima, J.Jpn. Soc. Co1our Mater, 65,
349(1992)
110 H.Oyabu, T.Asami, M.terada, Y.Aso, Y.Oda, J Jpn. Soc. Colour Mater, 65,
469 (1992)
111 Kumanotani, J .Prog.Org.Coat., 26, 163 (1995)
112. N. Niimum, T.Miya1<os11i, J.Onodera, T.Hjguchi, J.Ana1. App]. Pyr01., 37, 199

(1996)
113 Kumanotani, J Prog. Org. Coat., 34, 135 (1997)
114 E.Obataya, K.Umemura, M.NorimoIo, Y.Ohno, J.App1. Polym. Sci., 73, 1727
(1999)
115 J.Hong, H.K. Kim, J.O.Choi, J App]. Polym. Sci., 76, 1804 (2000).
116 M.M. Shirsalkar and M.A. Swasamban, Con'os.. Paint, 2, 203 (1979)
117 M.M. Shirsalkar and M.A. Swasamban, Corros. Control seminar Proc.1976,

Natl. Prod. Council, New Delhi (publ. 1977) p.329

118 M.T.Harvey, Cashew News Bu11.,1 1, 5-8 (1978)
119 D.N.Batia, N.J.Kazi and A.Asak. Foundry J., 21(6), 10-15 (1975)
120 B. Banargee, N.P.Suryanarayana and C.S. lnamadar, lndian Patent 142572 (1977)
121 A.Mahanwar and P.D.Ka1e, .1.App1.Po1ym.Sci., 61 912), 2107-21 1 1 (1996)

122 H.Masaki, J.Agri. Food Chem., 39(2), 418-421 (1991)

§‘hapter I iy _
J.K. Jain, J.Narayan., Timber Div. Associ. India, 37(2), 25-27 (1991); J.K.
Jain, J.Narayan., Timber Div. Associ. India, 37(4), 29-36 (1991
N.P.Suryanarayana and K.M. Joshy, J. Appl.Polym.Sci._, 8(3), l49l(1964)
K.D.Pathak, Indian J.Tech., l(1I), 433-34 (1963)
E.H.G. Seargent, British Patent 678019 (1952)
Zhisheng Dai, Anton Constantiniscu, Adarsh Dalal and Chris Ford, Cardolite
Corporation, New Jercy.
0.0. llomos, Y.M. Makame, L.L. Mkayala, Bulletin of the Chemical Society
of Ethiopia, 18(1), 81-90 (2004)
S.K.S. Parashar, D.K. Basu, M. Banaijee, Journal ofMetallurgy and Material
Science, 45(2), 97-101 (2003)
J.Lin, Tianra Chanwu Yanjiu Yu Kaif,l4(6), 24-26 (2002)
A.O.Attanasi, P.Filippone, Fuel, 83 (14-15), 2099-2100 (2004)
A.O.Attanasi, C.V. D‘Ornellar, L.R. Queirinz, Fuel, 82(l2), 1465-l469(2003)
D.Ras, P.K.Basu, P.Raghunathan , Joumal of Applied Polymer Science, 89
(7), 1959-1965 (2003)
A.C. Govindan, Chem.Engg.Wor1d, 32(1), 79-80 (1997)
R.1keda, M.Tanaka, H.Uyana, S.Kobayashi, Polymer, 43(12), 3475­
348l(2002)
VI). Athawale, N.J.Shetty, Surfac Coatings lntcrnational, 83(4), 168-172)
(2000)
T.C.Pathak, S.l.Agarwal and 1.Masood, Materials and Structure, 25(l50),
355-357 (1992)
RD. Shingle, P.P. Wadgaonkar, US Patent 6790993 (2003)
G-G. Fernandas, Joumal of Applied Polymer Science, 73(1), 29-34 (1999)
P.B.Chakrawarti, V.Mehta, Indian Joumal of Technology, 25(3), 109-113
(1987)
A.R.R. Menon, Journal ofFire Sciences, 15(1), 3-13 (1997)
D.V. Sudha, L.L. Mkayala, Journal of Scientific and Industrial Research, 38
(5-6), 186-191 (1995)
 Introduction

143 S.K.Sahoo, s.1<. Swain, o.1<. Mohapaha, S.Lenl<a, Angewandte

Makromolekulare Chemie, 233, 1-13 (1992)
144 M.Selvaraj, S.Guruviah, Bulletin of Electrochemistry, 5(9), 681-684 (I989)
I45 S. Muralikrishnan, P.Jayakrishnan, S.Guruviah, Bulletin of Electrochcmistry,
5(9), 674-676 (I989)
I46 Toshimi Shimizel, AIST Today Intemational Edition, No.10, http://
www.aist.go.jp
147 L.H.Sharpe, The materials, Processes and Design Methods for Assembly with
Adhesives Machine Design, 38( I9), 179-200 (1966)
148 E.M Petree, Plastics and Adhesives, Handbook of Plastics and Elastomers, Mc
Graw- Hill (1975).
149 N.J. De Lollis, Adhesives for Metals- Theory and Technology, Industrial
Press (1970)
150 I. Skiest, Handbook of adhesives, 2"“ edition, Van Nostrand Reinhold Co.
New York (1977).
151 N.J. De lollis, Adhesives and Adherends, Robert E. Krieger Publishing Co.
Huntigton (1980)
\
152 E.J Bruno (ed), Adhesives in modern manufacturing, Society ot
Manufacturing Engineers (1970)
153 A.G.Bayer, Baypren Chloroprinkaut Schuk, Technical bulletin.
I54 E.Schunck, Kunstharz-Nachrichten Hoechst, 4, 33 (1973)
I55. J .ShieIds, Adhesive Ilandbook, 2"‘! edition, Newnes-Butten-vorth, London (1976)
156 D.Narayanamurthy and R.S.Gupta, Rheo Acta I, 514 (1961)
157. CNSL Patents, Cashew export promotion council, Cochin Vol I & 2, 1964, 1976
158 D.Narayanamurthy and N.C. Jain, Forest Research Institute, Dehradun, Indian

Forest Leaflet No. 111 (1947)

I59 C.P. Dhamany, Paintindia, I9, 12 (1963)
I60 C.P.Dhamany, Paintindia, 21(6), 17 (I971)
I61. D. Narayanamurthy, T.R.N.Prasad and T.S. Rangamju, Res & Ind, 13, 134
(1968)
I62 D. Narayanamurthy and C .11. Pande, Composite Wood, 4(6), 97 (1957)
C.R. Bierman and J .D. Welks, US Patent 3879238 (1975)
H. Takagishi, M. Wakabayashi and Y.Takagi, F.Goto and E. Ohuno, Ger.
Offen. 2923314 (1979)
S.A. Perry, Chem. Paint, 9, 188 (1946)
A.R.R. Menon and C.K.S. Pillai, J.Adhes. Sci. Tech. 9(4), 443-451 (1995)
R.W Dyson, Engineering Polymers, Chapman & Hall, New York (1983)
M Morton, Rubber technology, Chapman & Hall (1995)
A.R.R Menon, C.K.S Pillai and G.B. Nando, Eur. Polym.J., 34, 7, 923-929
(1998)
A.R.R Menon, C.K.S Pillai and G.B. Nando, J. of Applied Polymer Science,
73, 813-818 (1999).
A.R.R Menon, C.K.S Pillai, G.B Nando, Joumal of Applied Polymer Science,
68, 1303-1311 (1998).
T.R Kukreja, R.C. Chanhan, S.Choe, P.P Kundu, Journal of Applied Polymer
Science, 87, 1574-78 (2003)
B. Banarge and C.S. lnamdas, Rubber India, 30(4), 13 (1978)
S.D. Shinkle, US Patent 2648613 (1953)
R.A. Rajapaske, W.A.S. Gunasena and K.B. Wijekoon, Polymer, 20, 887 (1978)
N.B. Fegade, Y.B. Sanghvi and W. Millns, Rubber lndia, 3391, 17 (1981)
N.D. Ghatge, B.M. Shindi, Elastomric 1 1 1(2),, 48-50 (1978)
A.R.R- Menon, .l.of Applied Polymer Science 65(11), 2183-2189 (1997)
A.R.R.Menon, J. of Fire Sciences 15(1), 3-13 (1997)
A.R.R.Menon, C.K.S. Pillai, Po1ym.Sci 2,657-661(1994)
A.R.R. Menon, C.K-S. Pillai and G.B. Nando, Polymer 39(17), 4033­
4036(1998)
J.M Manin, Handbook of Rubber Technology, Vol 1, CBS publishers and
distributors, New Delhi.
S.D. Vernekar,1ndianJ.Tech., 18(4), 1894), 170-172 (1980)
Ency. of Polymer Science and Technology, Vol 4, Interscience publishers,
John Wiley & sons, New York (1989)
C.P. Dliamany, Paintindia, 26, 19 (1979)
 Introduction

186 C.P. Dhamany and K.R. Singh, Paintindia, 29, 40 (1979)

187 C.K.S.Pi1lai, J.D.Sudha and A.G.Mathew, Indian Patent 314 (1987)
188 L.Y Mwaikambo, M.P Ansell, Composites Science and Technology, 63,
1297-1305 (2003)
189 E.T.N. Bisanda, W.O. Ogolu and J.V. Tesha, Cement and Concrete
Composites, 25, 593-598 (2003).
190 G. Joseph, Indian patent 146015 (1979).
191 S.P. Agarwal, S.K. Dolui, Res. Ind.. 40 (1), 1-4 (1995).
192 S.P. Agarwal, S.K. Dolui, Indian patent 186986 (2001)
193 B.C. Mitra, A.P. Manda], D. Soman, Indian patent 180002(l998)
194 T.Mathew, Indian patent 162132 (1988)
195 S.H. Aziz and M.P. ansell, Composite Science and Technology 64 (9), 1231-­
1238 (2004)
196 http://www.fifac.org.in/news/build.l\/lay 2002
197 http://www.bc.bangor.ac.u_1g May 2002
198 W. Klauditz, Development, state and economic significance of particleboard
manufacture, Hoiz-Roh-Werkstoff, 20, 1 -l 2 ( l 962)
199 B.G Heebink, R.A 1-lann and H. Haskell, Panicleboard quality as affected by
planar shaving geometry, Forest Prod J., 14, 486-94 (1964)
200 M Carroll, Whole wood and mixed species as raw material for particleboards,
Wash state Univ. Bull No 274 (1963)
201 W Klauditz and A Buro, The suitability of sawdust for the manufacture of
particleboards, Hol-Roh- Werkstoff, 20,19-26 (1962)
202 M Carrol, Relative effieiency of UF and PF resins in particleboard, Forest
Prod.J., 13, 113-l20(l963)
203 O. Wittman, The subsequent dissociation of fomialdehyde from particleboard,

Ho] Roh Werkstoff, 20,221-224 (1964)

204. J.Amthor, Holz Als Roh and Werkstoff, 30, 422 (1972)
205 L.Ranta , 11012 als Roh and Werkstoff, 36, 37 (1978)
206. H.A. Huber, Preservation of particleboard and hardboard with
pentachlorophcnol, Forest prod J ., 12, 228-301 (1962)
Chapter 1

207. W.Metzncr, H. Bollman , Holzschutz In: Ullmanns Encyclopadie D. Techn.

Chem. Vol 12, Ed Weinheim, Verlag Chemie (1976)
208. American National Standard for Panicleboard ANSI A. 208.] (NPA I993)
209. American Plywood Association, US product standard (1974).
210. Forest products laboratory, Wood Handbook: Wood as an engineering
material, Agric. Handbook 72 (Rev.), U.S Department of Agriculture
Washington D.C. (1987).
21]. J.A. Youngquist, Reconstified and treated products, Proceedings, Canfor
Symposium ( l 989).
212. M.V. Thanh, Eur. Polym. J., 285, 25 (3), (1989)
Chapter 2
SYNTHESIS OF CNSL RESINS

2.1 INTRODUCTION
2.2 QUALITY CONTROL TESTS FOR CNSL
a. Specific gravity
b. Insoluble matter
c. Volatile matter
d. Ash content
e. Iodine value
f. Polymerization time
g. Viscosity
h. Molecular weight
2.3 PREPARATION OF CNSL-HEXAMINE RESIN
2.3.] Raw materials
a. Hexainethylenetetramine
b. Phenol
c. CNSL
2.3.2 Procedure
2.4 CHARACTERIZATION
a. Gel time
b. Residual hexamine content
c. Melting point
d. Water insolubles
e. Molecular weight
ll. Differential scanning calorimetry
g. Thermogravimetric analysis
,Ch“P*‘T2 _ - - __ .. _
2.5 RESULTS AND DISCUSSION
2.5.1 Characterization of CNSL
2.5.2 Effect of phenol: formaldehyde ratio on the
properties of the resin
a. Gel time
b. Residual hexamine
c. Loss in weight on extraction with water
d. Melting point
e. Thennogravimetric analysis
f. Differential scanning calorimetry
2.5.3 Effect of CNSL: phenol ratio on the properties of the resin
a. Gel time
b. Residual hexamine
2.6 CONCLUSIONS
REFERENCES
 Synthesis of CNSL Resins

SYNTHESIS OF CNSL RESINS

2.1 INTRODUCTION

The most obvious and common method of obtaining polymeric material

from CNSL is the polycondensation with formaldehyde or formaldehyde
containing materials. In this work no attempt has been made to separate CNSL into
its components. Such a separation leads to considerable cost escalation. The
reaction of CNSL with formaldehyde is slow compared to that of phenol with
formaldehyde. Further, pure CNSL-HCHO resin is a brittle substance whose
mechanical properties are less impressive compared to phenol-HCHO resin (1). For
these reasons this study is based on a copolymer of CNSL and phenol obtained by
condensation with hexamine.

2.2 QUALITY CONTROL TESTS FOR CNSL (2)

CNSL is available from cashew nut processing centers as a byproduct. In

\
this study CNSL was procured from M/s Pierse Leslie Ltd., Kochi. The quality of
CNSL was ascertained by conducting tests prescribed in IS 840 — I964 (Table 2.1).
The results of these tests conducted on CNSL are summarized in Table 2.2.

a. Specific gravity
The specific gravity of CNSL was determined using a specific gravity bottle.
b. Insoluble matter

About 50g CNSL. was dissolved in four times its volume of toluene by
warming on a water bath. Then the solution was filtered and the weight of residue
was found.

c. Volatile matter

About 100g CNSL were heated at 205°C for 30 minutes. The loss in weight
was found.

d. Ash content

About 2g of CNSL was heated by means of a bumer until the ash was free
from carbonaceous matter.
_Cliapter2 g _ _ _ _ _ _
e. Iodine value
CNSL was treated in carbon tetrachloride medium with a known excess of
iodine monochloride solution in glacial acetic acid. The excess iodine
monochloride was treated with potassium iodide and the liberated iodine was
estimated by titration with sodium thiosulphate solution.
f. Polymerization time
CNSL was heated at 205°C with continuous stirring till foaming ceased.
Taken 5g of this dehydrated CNSL and 0.5 ml 25% solution of con. H2SO4 in
dietliyl sulphate in a test tube. The tube kept immersed in an oil bath at 176°C. The
time taken for the material to gel was taken as the polymerization time.

g. Viscosity
Viscosity of the sample was determined using Brookefield Viscometer (3)

h. Molecular weight
Both number average and weight average molecular weights were
determined by Gel Permeation Chromatography (GPC) using Hewlett Packard
(l08lB) equipment. Tetrahydrofuran was used as the solvent. A flow rate of
lml/min was employed and a refractive type detector was used.
Table 2.1
Indian Standards specification for CNSL
K - - Characteristic - l T Rsquitsmt 1­
g Specific gravity _ _ _ _ A _ _ M _ t _ _ (0.95-0.97 _ a
T Viscosity at 30"c,¢p (max) M 550 _t
f Mattcrinsolubleintoluene,%by wt.(max) _ _ _ i _ W 1.0 g W A
_Loss inwt. on heating,%'bywt. (max) i _ _ yg _ W W _l.0 _
{‘
v7.T_Ash,
y 7_7_ '7
Iodine 7%
_ ._ r by
T_ __' r_’7rwt.
value _ 7" (max)
7**
(max) ‘' 71.0
7_ 7 _~ _—A' __ 7. 'l'
7 7 at
, (a) Wijs method I Z50 ‘
‘‘‘ (b)(a)
Polymerization min (max) ‘t
Viscosity at 30°C, cp (min) H 30
4 l
C _ _.u;>_ §ata1y.1icni¢t1i@q_ _ _ _ _ _ -375 _ _;
Time, il
_ __ (0)) g_V_iscosity afieracicl washinig at 30°C, cpimillln L __ 200 ‘
 Synthegsgis of CNSL Resins

Table 2.2
Characteristics of CNSL
“Characteristics g it 0 g g R H P Results
iiiiii “P0954
1FSpecific gravity
Brookfield Viscosity, cp E g g pry 104
*PMoisture, % by weight (max) 0.92
+Matter insolublenin toluene, %lby weight (max) l 0.95
PL0ss in weight on heating, % by wt. g _ 0 0.93 fig g_
PAsh, % by wt. 1.023% pg __i
lodine value (Wigj=s)_g_ _ M my 249
*RPolymerization time, min l iiiiiii "R 10
Polymerization by viscosity method p
(Using Brool<_field visco1ne_tegr)3 cp 1 30
Polymerization at
_acidgwashing by30°C,
viscosity
cpg after
g 104
Number average molecular weight 235”
t Z average molecular weight __q H 3070
L
Weight average molecular weight _
Viscosity average molecular weight 406 it
506 t

fMw/Mn _g g__ 1 2.14 M

171./17,. g g_g 1.12 J
2.3 PREPARATION OF CNSL- HEXAMINE RESIN

Resoles and novolaks (4) the two well-known classes of polymers belonging
to the PF category can be synthesized from CNSL. Resoles are produced by
reacting phenol with a molar excess of formaldehyde under basic conditions.
Novolaks are produced by reacting a molar excess of phenol with formaldehyde
under acidic conditions.

Initial studies conducted on CNSL with hexamine yielded a highly plastic

mass. This condensation was found to require a much longer time than phenol with
hexamine. The product was rubbery with very little friability. Hence it was decided
to investigate the effect of copolymerizing CNSL with phenol by condensation
With hexamine in various proportions. Earlier attempts to synthesize CNS].­
formaldehyde (5) yielded ~a resin, which was employed for moulding particleboard
Chapter 2

directly. In the case of the copolymer CNSL-phenol-hexa, the final product was a
dry moulding composition.

2.3.1 Raw materials

a. Hexamethylenetetramine

Hexamine is a source of formaldehyde. Structure of hexamine is shown in

Fig 2.1.
N.

CH2 CH2 CH2

N N
N
CH2 CH2

CH2
Fig. 2.1 Structure of hexamethylenetetramine (hexamine)

It is highly soluble in water. Aqueous solutions are reasonably stable with

respect to reverse hydrolysis.

(cm). N4 + H20 601120 + 4NH3

Heat promotes the above hydrolysis reaction (6). Hexamine used for the
experiment was supplied by Laboratory and Industrial Chemicals, Cochin and was
of industrial grade. Purity of the sample was estimated by titration against
perchloric acid (6). Purity of hexamine was found out to be 94.62 %.

b. Phenol

Phenol of commercial grade was also supplied by Laboratory and Industrial

Chemicals, Cochin. Purity was estimated by treating phenol with an excess of
potassium bromate and potassium bromide; when bromination of the phenol was
complete the unreacted bromine was determined by adding excess potassium
iodide and back titrating the liberated iodine with standard sodium thiosulphate (7).
Purity of phenol was found out to be 95 %

64
 Synthesis of CNSL Resins

c. CNSL

Refined CNSL conforming to Indian Standard IS 840 (1964) was supplied

by Pierse Leslie Limited, Cochin in 200 L barrels. The average molecular weight
of CNSL was determined by Gel Permeation Chromatography (GPC) using
Hewlett Packard (1081 B) equipment. Tetrahydrofuran was used as the solvent.
The following results were obtained.
Number average molecular weight — 235
Weight average molecular weight - 506
Z Average molecular weight — 3070

2.3.2 Procedure

water condenser
stirrer
'2

thermometer

Fig. 2.2 Experimental set up for the preparation of resin

A three-necked lL RB flask equipped with a stirrer passing through a

mercury seal, a water condenser and a thermometer were employed for the
reaction. Heating was by an electric mantle with temperature control. The total
number of moles of phenolic substance was computed from knowledge of the
average molecular weight of CNSL. Hexamethylenetetramine and water were
taken in quantities in accordance with the hydrolysis of hexamethylenetetramine,
leading to the liberation of formaldehyde

(CH;)(, N4 + H20 6CH2O + 4NH3

65
 Chpp[er2__ _7A g_ g _ _ _ _ _ ___ __ __ _* ___. g___

Phenol, CNSL, hexamethylenetetramine and water were weighed out and

charged into the flask for a fixed CNSL: P ratio of l:l. The P/F mole ratios were
taken as 1: 2.9, l:2.5, 112.3, l:2.l, l:l.9, l:l.7, l:l.5, l:l.3, l:l.l and resins
prepared. The CNSL: P mole ratios were taken as 100: 0, 75: 25, 50:50, 25:75 and
0:100 for the case of P: F ratio l:2.9 and again resins prepared. Weight of phenol,
CNSL and water taken for synthesis for the resins having different P: F ratios are
shown in Table 2.3. Quantities taken for different CNSL: P ratios are shown in
Table 2.4. The reaction was carried out at 100°C for l.5 hours with continuous
stirring. The semi-solid product was removed from the flask and it was then
allowed to dry at room temperature for 3 days. The dried product was subsequently
ground to a powder and again dried for 24 hours.

As a variation to this procedure the resin after synthesis was discharged from
the RB flask into a glass dish and subsequently dried in an air oven for 2 hours at
' 100° C. Thereafter the resin was subjected to the same procedure employed in the
earlier ease. This additional step was aimed at completing any unfinished reaction
between hexamine and phenolic materials. The resin directly tested after synthesis
and room temperature drying is designated as Case A and that after oven heating as
Case B.

\ 1
Table 2.3
Weight of phenol, CNSL, hexa and water employed for synthesis of the resins
with different P/F ratios and a constant CNSL: P ratio of 1:1
fi_ _ _
icomossrfiow Weight bf’ "T Weightiof T We1ght0T T Weightof
;. - _P;F- _ - Phsnqltgml ._CN5l~(.sm): ; E6118: (sis)-
1_iI‘1;2.<;' 1‘ _100
j L; __ p_ I _1LC
100gig _ __ 7; 512950
Wale! 1m)
101 J . 4

1. _g112-5
113.1 _ 100g _ _1 g _ 10o_ g+_ 33.3 _. 12.06
- ; , _. 100 - 100 M .___ 4
_ __g 1;2.3 g_ {L1 iqo 1 100 _ T K 79.s_ K gy_ _19.2_6
1

_ 1;2.11_71001 100 T 7;.94___ 9.38 . ‘.

‘ *1;1.9 100 it T 5100‘ 7 0068.61 5 5 8.19 5

4’.­

*7 s 111.7‘ s @100 if if 5 ‘100 K T 559.05g T57)

7100. M 1
if _ 1;1.5 1” 5 1005 if 1100 1 5211‘ 5 T 6.69”
if 0 100 if 5100* if 7 45.165.8 5 ‘
1‘ _

4.91 .1A‘
 S_i;nthesis_ of CNSL K(i’5iIlS

Table 2. 4
Weight of phenol, CNSL, hexa and water employed for synthesis of the resins
with different CNSL/P ratios and a constant P: F ratio of l:2.9.
T COMPOSITION Weight ofl Weight or“ Weight of t Weight of l

-u-Z 1 * 0 100 28.79 3.69

CNSL/P4“? gr phenol (gm) l__CNSL_(gm) h6)@__(_gPl) watertggin) J

E |_ l
I00/0
it 7 7 25 l 75 l 39.48 l 5.08
25/75 7.85
75/25

50/50 50 50 p 50.33 6.46 5 ____...%_i;

75 i 25 56 an
0/100 100 0 9.25 71.99 .
2.4 CHARACTERIZATION

The following characterization studies were conducted on the synthesized

0

resin.

a. Gel time

Gel time of 0.5g resin at l50”C was determined by a hot plate method (8).
An electrically heated plate was maintained at 150°C. 0.5g resin was stoked with a
spatula until the sol-gel transition occurred. Sol-gel transition was indicated by
rapid increase in rubberiness or gel character of the resin. The gel time of the resin
was found (a) directly after synthesis and drying and also (b) after extraction with
water for 96 hours for removal of unreacted hexa.

b. Residual hexamine content

0.05 g resin was dissolved in 50ml glacial acetic acid and was titrated with
standardized 0. IN perchloric acid using 0.25% methyl violet as indicator until the
colour changed from violet to green (6).

C. Melting point

Melting point of the different samples was determined using a heated

capillary tube.
Cher?" 2, c _ c _
d. Water insolubles

Water insolubles of the samples after extracting with water were determined.

e. Molecular weight

Molecular weight ofthe resin was determined in one particular ease as a test
case. The number average and weight average molecular weights were measured
using GPC. A Hewlett Packard instrument employing a RI detector and
tetrahydrofuran as solvent (flow rate lml/ min) was employed.
Values obtained were
For resin with P: F ratio 1: 2.9 and processing time 1.5 hours
Number average molecular weight - 8 78
Weight average molecular weight - 3345
Z—average molecular weight -67166.
For resin with P: F ratio 1: 2.9 and processing time (1.5 + 2) hours
Number average molecular weight- I 0 79

f. Differential scanning calorimetry

Dift‘erential scanning calorimetry of the resin samples were done at a heating

rate IOOC/minute using Mettler calorimeter .

g. Thermogravimetrie analysis

Thermogravimetric analysis was done for the resin with P: F ratio l:2.9
using the instrument TGA Q50 V2.34 Build 127 in the temperature range 0-800°C.
2.5 RESULTS AND DISCUSSION

2.5.] Characterization of CNSL.

Characteristics of CNSL sample tested are shown in Table 2.1. The CNSL
sample tested for quality was found to be similar in properties to standard material
prescribed in the specification (Table 2.2).
 7 _ Syighesis of QVSL Resins
2.5.2 Effect of phenol: formaldehyde ratio on the properties of the resin
a. Gel time

The gel times obtained for Cases A and B are plotted in Fig. 2.3.

120 eeeeeee
-O-I
40 - —I—.CaseB
\_/

.._
80E .'_§\.__._*i.?_.?
60 y "'—‘* Case A
20

01:00.9 01:01.3 01:01.8 01:02.2 01:02.6 01:03.1

P:F ratio

Fig. 2.3 Variation of the gel time of the resin before

extraction as a function of P: F ratio

It is found that Case B leads to longer gel times than Case A. This may look
surprising as Case B corresponds to the product obtained after a longer processing
time. It is likely that a portion of unreacted hexamine decomposes during oven
heating. Formaldehyde liberated does not combine with the phenol groups because
of the ventilated atmosphere. This slows down the final crosslinking. This explains
the longer gel times for Case B. The effect of the ratio of phenol and formaldehyde
On the gel time is not very discernible. But the gel time appears to reach a
minimum around a molar ratio of l:l.9.

Fig. 2.4 shows the effect of composition on gel time after extracting the
powdered resin with water.
Chapterl 7 _ _ H _
E 7‘ ““““ V” H if 1 1

‘“’-.= -4--CaseA5
'1-A.
I

. --—I—CaseB
17

01:00.9 01:01.3 01:01.8 01:02.2 01:02.6 01:03.1

PJF ratio

Fig. 2.4 Variation of the gel time of the resin after

5
extraction as a function of P: F ratio
ln both Cases A and B one can safely assume that there is no free hexamine
or formaldehyde. In the absence of hexamine gel times for Case A are found to be

"_iIti‘1}iti;j
longer than for Case B. Crosslinking under these conditions is achieved by means
of methylol groups alone. Case B that has been processed for a longer time
contains a larger amount of methylol groups. This accounts for shorter gel times
exhibited by Case B.
b. Residual hexamine
Fig. 2.5 is the plot of phenol: formaldehyde ratio against volume of perchloric acid.

2251 . 1".“ C358 A

—I— Case B
i

1?

O ,_,.H________i______i_____.,..-,_____ . ___ -.-.._._ -... .777»

01300.9 01201.3 01:01.8 01202.2 01102.6 01:03.1
P:Frati0

Fig. 2.5 Variation of volume of perchloric acid before

extraction as a function of P: F ratio
-——
Synthesis of CNSL Resins

Fig 2.5 shows the volume of HCIO4 required to neutralize the resin. This
value indicates the extent of unreacted hexamine. There is a difference in residual
hexamine content between the two cases, though marginal.

,,-,-v-.~v~.,.-,»~___,,.__.______i____ ___ _ ..,,. _ ~ ~ ~,;;;;¢rf_.._,4,,.,\_—— — ——_---.-~-\~--~».----»-a~w-w‘---a--.--».----~v~~c~w~-.-“_»\

9.
‘L
weer ‘ Case A
""l- Case B

O :_ _________ _____ . Mi . .__.,._._.___,..,..,,..,___..,_____

01:00.9 01:01.3 01:01.8 01:02.2 01:02.6 01:03.1
P:F ratio

Fig. 2.6 Variation of volume of perchloric acid after

extraction as a function of P: F ratio

Fig 2.6 shows the volume of HCIO4 consumed after the samples were
extracted with water as a function of phenol: formaldehyde ratio. Both cases A and
B are found to give practically the same titre values. lt can be concluded that both

>.
Cases A and B lead to approximately the same extent of reaction.

c. Loss in weight on extraction with water

3 >'
Fig 2.7 shows the loss in weight on extraction with water.

._
15-5
20 . “w@%%@.,.m 1- _,,...,,\-\
I

i\
l

4-0,-Q 15
\; i

-0- Case A
l

-O-I
-Q-I

5 E

i
—I— Case B
i

0 ---ea 1% -- _ __,_7,_7;_.»,.»_»,;-_--;._-._;;1;_ _______ - _ '7' V _~,,__...._,.__._.,,,, ,,,,_­

938261
01.0 0. 01:01. 01:01. 01:02. 01:02. 01:03.

P:F ratio

Fig. 2.7 Variation of loss in weight on extraction with water

as a function of P- Ii‘ rafin
Chapter 2 _ a

s._o1;ti,
d. Melting point

_.
at
.
Case B shows a higher loss in weight compared to Case A. Water soluble
substances are more in the case of oven heating. Side reactions or the presence of
unreacted phenol or substantial amount of water-soluble oligomers only can
explain this behavior. In view of the large variety of compounds contained in
CNSL one can conclude that characterization of resin by this method may not be
very effective.

Fig. 2.8 is a plot of the melting point against phenol: formaldehyde ratio.

\1l
-0-’ ‘

Q1’ '
82 ................._e.__ ....... - H 2

70 if 0 ~ rs e use —e
1

01:00.9 01:01.3 01:01.8 01:02.2 01:02.6 01:03.1

P:F ratio

Fig. 2.8 Variation of melting point as a function of P: F ratio

t.

ti

11

Melting point remains constant at 70°C until a stoichiometric ratio of l:2.3 is

reached. There is a steady increase in melting point at l:2.5 reaching 80°C at l: 2.7.
A certain amount of condensation between resole molecules can be expected at
high formaldehyde contents. This can lead to increase in molecular weight and a
corresponding rise in melting point. This effect becomes noticeable at a
stochiometric ratio of l: 2.3. The effect seens to level off at l:2.7 and 800C.
 ‘I‘tL: ­
Synthesis of CNSL? Resins

e. Thermogravimetric analysis

i' ‘U-UPC
/N 10 '
lZC—-* -u ~~ - — ~42
TGA

‘u
1.
m1:
1
‘F
.| 4.
U
i" ‘ >­
. .| I‘
.

-in
3 -_ - nuns U,
1

404?
1
‘N
4
.
I
* T 1
.' §U"C
107' —-_— _—_ ._-—__ - _; Lo
I

‘I

°T ‘i ‘ 115 F‘ '""""'""$o ”'“”' ""22 J» ' ' F" J5‘

' -0
Tsnpemhan ('0)

Fig. 2.9 TGA of resin with P: F ratio 1: 2.9

Fig 2.9 shows the TGA of resin with P: F ratio l:2.9. The peak maxima and
q­

b
I

the corresponding temperatures are given in Table 2.1 1.

Table 2.11
Degradation characteristics of resin with P: F ratio 122.9
ur IInitial Temperaturet _of_, iFinal
_ _ Maximum I_
Residue
1temperature
2 _ degradation . at 800 (. r
i decomposition 1 maximum rate _ 1 decomposition U __
A of weight loss O _ 1 temperature 2 0
i 0Tiw(0L)
L rateTmax(
(A)/min)
C) ; ; T;(
O \ L)
c (/0) ,
100 F 446.68 if 11 i 500 MWFQQ
f. Differential scanning calorimetry

The DSC of resin with different P: F ratios are given in Fig. 210- 2.13. As
formaldehyde content increases cure temperature increases. At high formaldehyde
Chapter 2

content high methylol groups are present in the resin. The temperature of onset of
curing (Ti), peak temperature and the temperature indicating the end of exotherm

i\
are given in Table 2. I 2.

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Fig. 2.10 DSC of resin with P: F ratio 1:2.9

? Integration 1
icardenol-iornaidehgae <1=§.1>‘ ' 7 rat; 12107.00: 0§c . liIILEl
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1- q--:-::2:;:-:2}!
-Ii-:g:22Z;1;;Z;'
1|,,=:==1;:f::?::;:!:;;-"
-:==;=!=-¢=,,!:= ;:;;­ -5,; ‘‘,
;--!=--='M=E2=E.Fz{??\
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i5‘252.
air ii _:sue.
__ __ 1
'1: if
i 4% fri Ff" 7 *7 * ’.*4 —rj y—'—'*p I * '' v" ‘F
' '­

Fig. 2.11 nsc of resin with P: F ratio 1=2-3

7 A Synthesis of CNSL Resms
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S5!
‘T - *T*“f 1 h=Tw~—F:—Tm i——+~—¥+<1 QrH*r 1 1 ­
— ~ — ~— ~ — ~—_. .__ _ 4* .—~ . _ - _ __ ; _ .__ .,_,_,. . 1
Fig. 2.13 DSC of resin with P: F ratio l: 1.1
Chapter2 _m __ _ _ J %
Table 2.12

.l Exothermal
__ — ._P k_T._.._ . ._ . i
Differential scanning calorimetry of the resin with different P/F ratios

Temperature
COMPOSITION .1 heat 01 cure , ea 0 5”“ 1Il(l1C8't1I1g end of
;__m p p p AHp(.l/g) 1 remp( C) p ( C) _1 exotherm (Tf)
112.9 \ 195.5 222.7 165 . 285

2852 J,
ty. _ _ .
A 112.3 175.2
i 1:11 15s _ |[ i 220 1 165
210.3 f 150 1 270 "
no l:l.l
__ _A c98I. r H We _ 202.8 155 265
_ __ .

2.5.3 Effect of CNSL: phenol ratio on the properties of the resin

ia. Gel time

.’ .
1 CNSL: P
7 .W!
L
Table 2.13
Gel time of resin with different CNSL/P ratios

Gel time

100:0 1 45 minutes

75:25 15 minutes
2+

50:50 1 I4 seconds

25:75 102 seconds

-1
0: I00 . 80 seconds

Table 2.13 shows the variation of gel time with different CNSL/P ratios. As
CNSI. content decreases, gel time sharply decreases. Reaction of CNSL is slow
compared to phenol because of stmctural difference. So the gel time of resin
decreases as CNSL content decreases
 Synthesis of CNSL Resins

b, Residual hexamine
Table 2.14
Residual hexamine content of resin with different CNSL/P ratios

P;CNSL 6 \g/golume of HClO4 (ml)

100:0 1.3
75: 25 3.1
50; 50 22.5
I 25; 75 22.7 y
y 0; 100 1 22.1
_[_ .._

Table 2.14 shows the variation of resin with different CNSL/P ratios. As
CNSL content increases, volume of perchlorie acid increases. Reaction of CNSL is
slow compared to phenol. Hence residual hexamine is likely to be more when
CNSL is used. Volume of perehloric acid which is a measure of unreaetcd hexa
increases as CNSL content increases.
2.6 CONCLUSIONS

CNSL used_for this study eonfoirns to IS specifications. CNSL has Mn

=235,1Tiw = 506, M1 = 3070.

CNSL- phenol- formaldehyde copolymer can be synthesized by

condensation between CNSL, phenol and formaldehyde. Resin prepared with a
stoichiometric ratio ofP: F = 112.9 and CNSL: P = 1:1 is found to have M; = 835,
MW = 3345, My = 67166, Decomposition temperature = 447°C. Both methods
(Case A and Case B) are found to give resins of comparable properties.
Resole resin prepared from CNSL and phenol by condensation with
formaldehyde has a melting point of 70 to 80°C. The melting point sharply increases
from 70 to 800C between stoichiometric ratios of 112.3 and 1: 2.7 between phenol and
formaldehyde. The resin on crosslinking shows increasing values of heat of reaction
and peak exothermic temperature with increasing formaldehyde content.

Of the two methods employed for the preparation of the resin the second
method (Case B) involving an oven-heating step after condensation in an RB flask
leads to longer cure times. However on extraction with water, resin prepared by the
Second method (Case B) is found to give a shorter cure time.
Ch???" 2 _ _ _ _ M E
REFERENCES
1. P.A. Mahanwar, P.D. Kale, J. Applied Polymer Science, 61(2), 2107 (1996).
2. IS 840~1964.
3. ASTM D 2393-86.

4. L.H. Backland, J.Ind.Eng.Chem.,1 (3), 149-161 (1909).

5. P.A.Mahanwar, P.D.Kale, J. of Applied Polymer Science 61(2), 2107 (1996)
6. J. Fritz, Anal.Chem., 22, I028 (1950).
7. J. Haslam, H.A. Willis, Identification and Analysis of Plastics, Ist edition,
Iliffe Books, London (1965).

8. L Leiber, Encyclopedia of Polymer Science and Technology, Vol ll, John

Wiley & Sons lnc., USA (1989)
Chapter 3
DEVELOPMENT OF CNSL BASED ADHESIVES

3.1 INTRODUCTION
3.2 EXPERIMENTAL
3.2.1 Materials
3.2.2 Adhesive preparation
3.2.3 Adhesive formulation
3.2.4 Substrate preparation
3.2.5 Surface preparation
3.2.6 Application &curing
3.2.7 Parameters for evaluating adhesive performance
a. Resin content
b. P: F ratio of resin
c. CNSL: P ratio of resin
d. Processing time
e. Coupling agent
f. Fillers
g. Sulphur
h. Surface treatment
3.2.8 Adhesive performance
3.3 RESULTS AND DISCUSSION
3.3.1 Al-Al bonding
a. Shear strength
l. Effect of cure time and cure temperature
2. Effect of P: F ratio of resin
3. Effect ofCNSL: P ratio of resin
4. Effect of processing time
i. Resin with P: F ratio l: 2.9
ii. Resin with P; F ratio l: l.l
_Chiaptgr3 _ _ _ j __ __ _
b. Peel strength
1. Effect of cure time
2. Effect of P: F ratio of resin
3. Effect of CNSL: P ratio
c. Effect of coupling agent on shear/ peel strength
d. Effect of carbon black on shear/ peel strength
e. Effect of silica on shear/ peel strength
f. Effect of sulphur on shear/ peel strength
3.3.2 Rubber-metal bonding
a. Shear strength
1. Effect of P: F ratio of resin
2. Effect of CNSL: P ratio of resin
b. Peel strength
1. Effect of P: F ratio of resin
2. Effect of CNSL: P ratio of resin
c. Effect of coupling agent on shear/ peel strength
d. Effect of carbon black on shear/ peel strength
e. Effect of silica on shear/ peel strength
f. Effect of sulphur on shear/ peel strength
3.3.3 Rubber-rubber bonding
a. Shear strength
l. Effect of P: F ratio of resin
2. Effect of CNSL: P ratio of resin
b. Peel strength
l. Effect ofP: F ratio of resin
2. Effect of CNSL: P ratio of resin
c. Effect of coupling agent on shear/ peel strength
d. Effect of carbon black on shear/ peel strength
e. Effect ofsilica on shear/ peel strength
f. Effect of sulphur on shear/ peel strength
3.4 CONCLUSIONS
REFERENCES
 Development of CNSL Base¢_i_Adhesives

DEVELOPMENT OF CNSL BASED ADH ESIVES

3.1 INTRODUCTION

The adhesive formulations investigated in this study consist of CNSL based

resins in combination with neoprene rubber. Rubber based adhesives have superior
elongation, toughness and flexibility. They are particularly advantageous for joints
in flexure. Neoprene adhesives have high bond strength, creep resistance,
durability, flexibility, chemical resistance and resistance to burning. Temperature
and solvent resistance of neoprene adhesives are considerably increased by
additional crosslinking with thermosets especially phenolic resin, which also
improves tack and adhesion. It also inhibits HCI formation during the ageing of
neoprene and imparts viscosity stability (1,2). Adhesion to most materials is good
due to the marked polarity of the phenolic structure. When phenolic resins are
combined with elastomers, the characteristic properties of both can be utilized and
specific requirements met by varying the concentration of the resins. Toughening
action of such polymer blends is attributed to chemical reaction, but even more to
the morphology of the cured system. Because of limited solubility of the
elastomeric component a discrete, well dispersed, discontinuous phase develops in
the cured phenolic matrix. The crack propagation is considerably minimized by the
two-phase system and impact strength improved (3). Disadvantages of phenolic
resin are its brittleness and the high curing temperature and pressure required.

CNSL is a desirable starting material for adhesive formulations due to its

renewable nature, high polarity, inherent tackiness of phenolic materials and the
ease with which liquid to solid conversions can be accomplished in CNSL based
resin. This study aims to investigate the effect of incorporation of CNSL based
phenolic heat curable resin on neoprene adhesive formulations.

3.2 EXPERIMENTAL

3.2.1 Materials
3- Isobutylene-Isoprene rubber (IIR) was supplied by Bayer Polymers, India.
Chapter 3 _ i _
b. Styrene-Butadiene Rubber (SBR 1502) was obtained from Japan Synthetic
Rubbers Co.Ltd., Tokyo.
c. Chloroprene (CR W) was supplied by DuPont, Akron, Ohio. Mooney
viscosity ML (l+4) was 47
d. Zinc oxide (acivator) was supplied by M/s Meta Zinc Limited, Bombay. Heat
loss, max (Zhrs at 100°C) — 0.5%
e. Magnesium oxide (MgO) was supplied by Fine Chemicals Ltd., Mumbai.
f. Precipitated silica used was of commercial grade supplied by Sameera
Chemicals, Kottayam.
g. Carbon black (HAF N330) was obtained from Philip Carbon Black limited,
Kochi, India.
h. Toluene was supplied by Fine Chemicals Ltd., Mumbai
i. Trichloroethylene was supplied by E. Merk Limited, India.

3.2.2 Adhesive preparation

Neoprene chips were milled on a two-roll mill at close nip for about 7
minutes to improve solubility. The masticatcd rubber was then cut to pieces and
dissolved in toluene to get a CR solution in toluene. The prepared resin was
dissolved in this CR adhesive solution. Details of preparation of resin are given in
section 2.3. The resin concentration was varied from 25 -75 phr.

3.2.3 Adhesive formulation

The basic formulation consists of the following ingredients

CR W - 100
M gO - 4 phr
ZnO - 5 phr
Resin - 25-75 phr
Tolucne- 250 ml

Experiments were done to study the effect of resin content, P: F ratio of the
resin and CNSL: P ratio of resin on the adhesive properties. In addition, various
tillers and adhesion promoters were incorporated into the formulation to study the
effect on adhesive properties.
¢_— _ Development of CNSL Based Adhesives

Phenolic resin reacts with MgO. Magnesium is coordinately and chelatively

bound to the hydroxyls of the methylol and phenolic groups, resulting in a three­
dimensional system. This soluble MgO complex promotes solvent release and
improve cohesive strength. The remaining MgO serves as an acceptor for I-1C1
released by neoprene. ZnO is included as a curing agent and acid acceptor (2, 4).
3.2.4 Substrate preparation
The substrates chosen for study were aluminium and two different
elastomers. The elastomers selected were butyl rubber and SBR. Most of the rubber
-to - rubber bonding (R-R) studies were done on llR-HR specimens. A limited
number of studies were done on SBR-SBR specimens.

The compounding of rubber was done on a conventional laboratory size two­

roll mil] at a friction ratio l: L25 and according to ASTM D 3188-00 (5) for HR
and according to ASTM D 3 l 85-99 (6) for SBR

The formulation used for HR is given in Table 3.1 and for SBR is given in
Table 3.2.
Table 3.1
Formulation used for [IR
[IR 100 g
Z -----,-pZI1Qp. __| ......... _,, 3
f_= Stearic Acid I g M]
T Sulphur ‘ 1.75
Carbon Black (HAP) 50 1
f _Tl\4TD
MBTS 0.51
t SP 4
3 Paraffmicoil if 35
Chapter 3 H
Table 3.2
Formulation used for SBR
_j SBR 100 c y
ZnO _ 4 ._ ll
Steafic acidis L 1

Carbon black (HAP) . 5(l i

P g Aromaticoil l0 _ *
L _ MBTS g j 0.5 Li
I 'TMTD
,l
I
'Sulphur
' l i 0.5
.IS5 l

t_ _. SP l 4
Cure time of the compound was determined at 150°C on a Goettfeit
Elastograph (Model 67.85). Vulcanization to optimum cure time was carried out in
an elecrically-heated hydraulic press at 1500C. The sheet was cut into strips of 100
x 25 x 2 mm size.
I-G
Aluminium strips of size 100 mm x 25 mm were machined from {-}.—8" mm
0'52
thick sheets to serve as metal substrates for shear test and 0:48 mm thick sheets for
peel test.

3.2.5 Surface preparation

Surface preparation was carried out to provide an adherent surface
conducive to the development of strong and durable adhesive joints. It is desirable
to have the basic adherend material exposed directly to the adhesive. Surface
preparation for aluminium plates was done by abrasion using 100 grit emery paper
followed by solvent degreasing using trichloroethylene. For butyl and SBR
substrates abrasion followed by solvent wipe using toluene was carried out prior to
application of the adhesive.
—_— _ Development of CNSL, Based Adhesives

A limited number of Al samples were subjected to surface treatment.

Sulphuric acid- dichromate etch (ASTM D 2656-79) (7) was done by immersing
the aluminium substrate in a solution containing 30 parts by weight (pbw) water,
10 pbw sulphuric acid and l pbw sodium dichromate for l0 minutes at 600C and
then it is washed with water and dried.

3.2.6 Application and curing

Alter surface treatment, if any, the strips were coated with the adhesive. A
single adhesive layer (approximately 0.1mm thick) was applied on each substrate
on an area of 2.5 x 2.5 cms. The solvents were dried out and the substrates joined.
The adhesive was then cured in a hydraulic press.

3.2.7 Parameters for evaluating adhesive performance

The performance of adhesive joints was evaluated by measuring the peel and
shear strength. Peel and shear strength were tested after varying each of the
following parameters.

and 75 phr. 0 0 0
a. Resin content: The concentration of resin was varied as 25, 35, 45, 55. 65

b. P: F ratio of resin: l:2.9, 1: 2.3, l:l.7 and l:1.l.

c. CNSL: P ratio of resin: l00:0, 75:25, 50:50, 25:75 and 0:100
d. Processing time of resin: 15, 30, 45, 60 and 90 minutes.
6. Coupling agent: Silane adhesion promoter 3- aminopropyl triethoxy silane in
varying concentrations (0, 0.25, 0.5, 0.75, l, 1.25, 1.5 phr)
f. Fillers: Carbon black and silica in varying concentrations (2, 4, 6, 8, l0 phr)
g. Sulphur: Sulphur in varying concentrations (0, 0.5, 1, 1.5, 2, 2.5, 3 phr)
11. Surface treatment: Sulphuric acid~ dichromate etch treatment was done for
aluminium samples.
(lhapt§r_3____ W A p j _ i _ __ J J ___ _
3.2.8 Adhesive performance
Peel strength was determined as per ASTM D 903-98 (2004) (8) and shear
strength as per ASTM D I002-49 (1981) (9) with erosshead speed of50mm/minute
at room temperature using Universal Testing Machine.

1013

ts _ s -4
Ia_-__ _ _ _ -___ s___- __.___ __J_§.17T_lQQ_ :1 T Ll L; Q I1

4-Hr

t i it i ii
‘J: J: ‘Z K‘ ii" 2511.15 i 7
t*—"*’1

L1 t_t t tTs ____

.e¢¢e
Fig. 3.1 Shear test specimen (Dimensions in mms)

1 Os
:iQ;l_L_l_:._L ____ __.___ s___ ___ ______ _- .__ I

it i i i i H
4<._-J; e--~»_--_---~ -~- - ——+4-513

Fig. 3.2 Peel test specimen (Dimensions in mms)

 Development of CNSL Based Adhesives

3. 3 RESULTS AND DISCUSSION

3.3.1. Al-Al bonding
a. Shear strength

1, E [feet of cure time and cure temperature

Fig 3.3 shows the variation of shear strength of Al-A] bonds with cure time
of the adhesives at different cure temperatures (120, 130, 140, 150 and l60(()

3 t..........-........._......._...................._.~._...-......._........_..._.........-...._.__ .......... ......... .... ... ............ ..}

0% i

i
1

l
2
I
-—§—-120
—-I-130
—-I-140
—-)(—15O
1, i

-9!--160
1

O123
0 S S-SS. S S S S- S See __,:eSSt..St.STT

Cure time (hours)

5

Fig. 3.3 Variation of shear strength of Al-Al bonding with cure time
for different temperatures. Resin with P: F ratio ]:2.9, CNSL: P ratio 1 1 and
45 phr resin content was used.

The adhesive cured at 1400C and 2.5 hours shows maximum shear strength
At lower temperatures curing may not be complete and at higher temperatures
shear strength decreases due to over cure. The optimum cure temperature and eure
time of 1400C and 2.5 hours were selected for further studies.
Chapter3g _" _ _ 7 g
I-§ I l"
2. Effect of P: F ratio of resin

3 ‘__...,,....._.__.....-.....,-.._.-.........,........_ ------------- ._.....,“,,..___ --------------------- ..~_ .................. ....v..~.... .......... -~ ............... .,.~.-\--.-.__

~_., 2 \ —§— PIF 122.9

.. "t ._ — as‘ ‘J —A—P:F 1:11
1 F ->(——P:F1:1.1
0 20 40 60 80
la -—I-— P:F 1:2.3

Resin content (phr)

Fig. 3.4 Variation of shear strength of Al-Al bonds with resin content for
different P: F ratios. Resin with CNSL: P ratio l:1 was used.

Fig. 3.4 shows the variation of shear strength of Al-Al bonds with resin
content for resin containing different P: F ratios (Here P refers to the total phenolic
matter viz. the phenol and CNSL).

As the resin content increases shear strength increases, it reaches a

maximum and then decreases. As the resin content increases, brittleness of the
adhesive layer enhances. Also there is non unifomi wetting of the surface. The
highest shear strength is obtained for 45 phr resin content.

Higher methylol content due to higher proportions of formaldehyde can give

higher polarity and better bonding. Resin with P: F ratio l:2.9 shows high shear
values compared to resins with lower P/F ratios. Phenolic resin possesses
exceptional adhesive properties on metal surfaces and can form a relatively strong
chemical bond by virtue of the complex formation of O- methyl hydroxyl phenol
with the hydrated metal oxide surface (10) which imparts good bonding
characteristics. Phenol dissociates on aluminium oxide to form aluminium
phenoxide (l I), which also improves bonding characteristics. ln sulphur
vulcanized rubbers there is sulphur-metal interaction. (12). This also improves
bonding strength. Phenolic resin also leads to polar- polar interaction with the
metal surface. Polar oxygen groups in the phenolic resin are capable of strong
interaction with the metal surface.
 D¢'ve1vPm@"* of @151 Based 4f"'F1€?’?$

l
;I 5.
3. Effect of CNSL: P ratio of resin

--O-—
._____a _,.,;_._.__;: __ :___:_.;.__; _,_T,.,,., _,_,_,_ ,_ ,...,_- 1 I‘ w-.~_---wv--w M ».~ vuwcu II\!I\ .-ww ... vv -- A -~..-. ~_-. vw »-~ I15 . Q . , ,;

CNSL/P
-1- CNSL/P
i —X—-
100/O
1; -1- CNSL/P 75/25
o CNSL/P50/so
25/75
00 20 40t 60 80t Resin content(phr)

Fig. 3.5 Variation of shear strength with resin content for different CNSL/P
'2
>
—3K— CNSL/P O/100

ratios. Resin with P: F ratio=l :2.9 was used

Fig. 3.5 shows the variation of shear strength of Al-Al bonds with resin
content for resin with different CNSL: P ratios. As the CNSL content increases the
value of shear strength decreases. CNSL has a long side chain which induces a
plasticizing action. This may decrease the shear strength of the adhesive. However
81 25% CNSL content, the values are close to those obtained by using pure
phenolic resin.
 i
1.
ll
Qhantgrji _ -_ _ s ___-__ _- - _
4. E jfect of processin g time
i. Resin with P: F ratio l:2.9

3 rp----=4;-uu-----.---q-9»-.--~»»---.—-»<»ea-mu.--.._¢';;;-; —_-_--_i—_-;;;_<_---...T;¢;;;?4—_-~_»_ _4;¢-_=_?|u--~v.--iv-:;T

l

t —-O-15
-—I—60

0 20 40 60 80 Resin content (phr)

Fig. 3.6 Variation of shear strength of Al-Al bonds with processing

time. Resin with P: F =1: 2.9 and CNSL: P= 1:1 was used.

Fi g. 3.6 shows the variation of shear strength of Al-Al bonds with processing
time ofthe resin with P: F =l:2.9. As the processing time increases shear strength
decreases because the molecular weight of the resin reaches excessively large
values. The best properties are observed for the resin processed for 15 minutes.

1.6 :‘
ii. Resin with P: F ratio l:l.l

V1.4»
1.2 c f-0-30
-4-15
M

1.8 2?
J?

15 —m-45
. lg —->e—60 . -——X——9O

0 20 40 60 80 Resin content (phr)

Fig. 3.7 Variation of shear strength of Al-AI bonds with processing

time. Resin with P: F =1:].l and CNSL: P ratio ==] :1
 Development of QNSL Based Adhesives

Fig. 3.7 shows the variation of shear strength of A1 -—Al bonds with
processing time for the resin containing P: F ratio l:l.l. In this case also as the

l.
processing time increases shear strength decreases. For this P: F ratio also (1: 1.1),
the optimum processing time appears to be 15 minutes. A prolonged processing
time in this case leads to fall in shear strength.

5. Effect of surface treatment

5Z

\/
j 4
,_,1 iti—O—
—I—without
with stst
l

0 20 40 60 80
6 ’ _ _ ___-_—m.—.?:_r:.T.i_<.<.—?—uuwau-n--~—-mn-@¢%-v»-v-.---us--up-uuuuvwu-an-1,--\--\c-ama-v.¢uuuv--vw-v/-\uI

Resin content (phr)

Fig. 3.8 Variation of shear strength of Al-AI bonds with surface treatment
(ST- surface treatment). Resin with P: F ratio l:2.9 and CNSL: P ratio 1:1 was
used

Fig. 3.8 shows the effect of sulphuric acid- dichromate etch (FPL etch) on
shear strength of Al-Al bonds. This treatment increases the shear strength between
Al and Al. Sulphuric acid~ sodium dichromate etch treatment for aluminium
Produces a strong adherend layer of hydrated oxide [5- A1303 3}-‘I20 which increases
the adhesive strength (1). Both cases have a maximum value of shear strength at 45
Phf of resin.
 iZrJ
Chapter3__ A i _ W # *_ __ Hf _*_ i_ j : i % _ Q

b. Peel strength

is i
I. Effect of cure time

3 |,-.-.....-~...._. !¢\ v.» »- -w_._._.....-.......,_.__,

.-\2,5i <

3
\.-/
O-at

Q‘!
‘­ 11

O 0.5 1 1.5 2 2.5 3 3.5

0 ;____-.______.._____. ____- _.-_ __ e_._____ ,__._._ é.__e,_ __..__-..._._.-.___.__._.__i

Cure time (minutes)

Fig. 3.9 Variation of peel strength of Al-Al bonds with cure time. Resin with P:
F ratio l:2.9, CNSL: P ratio 1:1 and resin content 45 phr was used

F i g. 3.9 shows the variation of peel strength with cure time of the adhesive at
l40°C. Optimum peel strength was obtained at 2.5 hours. This agrees with the
results obtained for maximum shear strength.
 Development of§NSL Based Adlzesittes

2_ Effect 0fP: F ratio of resin

. I:
4
.1 -0-P:F1:2.9
..__ __,:________________ ______v_,,___. .__. ~ ~ ‘*2-_~_?_-_:-_—_-_-_-:" »~~------@—mm

‘ -——I-—P:F 122-3
QJ —l—-P:F 1:1.7
, -—>(—P:F 111.1

it

O 20 40 60 80
Resin content (phr)

Fig. 3.10 Variation of peel strength of Al-Al bonds with resin content for
different P: F ratios. Resin with CNSL: P ratio l:I was used.

Fig. 3.10 shows the variation ofpeel strength of Al-Al bonds with different
P/F ratios. As the resin content increases peel strength increases, reaches a
maximum value and then decreases. The enhancement in peel strength can be due
to the increase in specific adhesion with increasing resin content. As the resin
content increases beyond the optimum level, the flexibility of the system
decreases, resulting in a reduction in peel strength. Resin with P: F ratio l:2.9
shows high peel values compared to resin with higher P/F ratios. As the
formaldehyde content increases, the methylol content increases and this leads to
better bonding. Maximum peel strength is obtained for adhesive formulations
having 55 phr resin content.
Qrflvtfl 3

3. Effect of CNSL: P ratio of resin

4 ~ {{{{{{{{ at
3.5 ‘
an 31I

11 . //'
M‘ .‘ W

—&- CNSL/P 100/0

§.v ‘
l

-—I—-CNSL/P 75/25
!

i\

21 U
V

‘.
—i-—— CNSL/P 50/50
-—-)(— CNSL/P 25/75
11

it

— or li

1.
—-¥— CNSL/P 0/100
i.
..
V

ii

0.5 9

0 20 40 60 80
1

Resin content tphr)

Fig. 3.11 Variation of peel strength of Al-Al bonds with resin content for
different CNSL/P ratios. Resin with P: F ratio l:2.9 was used.

Fig. 3.11 shows the variation of peel strength of Al-Al bonds with different
CNSL/P ratios. As the CNSL content increases the value of peel strength
decreases. But it is possible to replace about 25% ofphenol with CNSL without too
much loss of peel strength.
 Development of CNSL Based Ad!-zesirqes

'c. Effect of coupling agent on shearl peel strength

i .»,-......-0..-.»._,~ .4 ...... ._._,___._,_,,.,,_, ........ --U-~c~»-—--—~ --------- -~-~"*""-'*"°°“'°-°""""_"‘“"""'-"' *

@­

0 0.5 1 1.5 2
3
3

_,_:___ _ ,, _.___.*..=__..... .*. _ V V V K. 3

Coupling agent (phr)

-0-— Shear strength (MPa) —l—- Peel strength (N/nm)

Fig. 3.12 Effect of coupling agent on Al-Al bonding. Resin with

P: F ratio 1: 2.9, CNSL: P ratio 1:1 and resin content 45 phr was used.

Fig. 3.12 shows the variation of shear strength of /\l—Al bonds and peel
strength of Al-Al bonds in the presence of the coupling agent 3- amino propyl
triethoxy silane. Addition of the silane improves the bonding strength of Al-Al
specimens considerably. The effect of coupling agent is more noticeable in the case
of shear strength. Coupling agents have the ability to migrate to the interface and
improve adhesion. Silane coupling agent above 1.25 phr shows very good
improvement in bonding strength values. Chemical bonds are formed between the
metal oxide and siloxane. (13) Silanes can form strongly adsorbed polysiloxane
films on metal surface. Polysiloxane has an open porous structure and the liquid
adhesive can penetrate into them and then harden to fonn an interpenetrating inter
Phase region. Another reason for the increase in bond strength on addition of
silane, may be the reaction of the amino functional group in the silane coupling
agent with the adhesive resin (13). The coupling agent also improves the adhesion
by improving the level of wetting. (14).
C3rapter§ H ._?

d. Effect of carbon black on shearl peel strength

Effect of carbon black on Al-Al bonding

_. _ I I— <t 5
. ---,.-.-.._._-4-mm-.._.€-»M~¢-o-.---.~-.....---_¢~.--_-_---..i.-“-»-w___-.~».-..._.i--_-,-~ ...... IZ\~v~ ...... _----r-.,-.~..,--.¢-.-~.».~.i,....,..._._,,._‘
l

O 2 4 6 8 10 12
Carbon black (phr)
-»- Shear strength Ki;/tn (MPa)“ 4- Peel strength AI-Al(N/m m)
Fig. 3.13 Effect of carbon black on Al-Al bonding. Resin with P: F
ratio 1: 2.9, CNSL: P ratio 1:] and resin content 45 phr was used.

Fig. 3.13 shows the variation of shear strength and peel strength of Al-Al
bonds with carbon black content. Carbon black is added to reduce the cost, increase
the specific gravity and raise the viscosity of the adhesive formulation (15). The
reinforcing quality of carbon black improves the shear strength marginally up to
about 4 phr. After that there is a retum to the original level. In general, carbon
black has only moderate effect on shear and peel strengths

e. Effect of silica on shearl peel strength

__..-.--\~.»»\.~__.~.-.»~¢~-\~i-.----~\-..~ -_.»---~».___---»-.~_-_-.-»~-~---.---.,“-a“. -_-,, -..-..,..._ __,,. ..,.-- ~ ~. -.. \,.\ ,___, _,__,.,_,.,,.__ ___ __ ,,,_,_,

_
*.“‘ i" .
0 2 4 6 8 10 12 Silica (phr)

-0- Shear strength Al-AI (MPa) —-l— Peel Slfenglh Al-A|(N/I'r‘m)

Fig. 3.14 Effect of silica on Al-Al bonding. Resin with P: F ratio l:2.9, CNSL:
P ratio 1:1 and resin content 45 phr was used.
 Development 0fgCNSL Based Adhesives

Fig. 3.14 shows the variation of shear strength and peel strength of Al-Al
bonds with silica content. Silica content above 4 phr leads to some increase in
shear strength. Peel strength on the other hand is reduced by the presence of silica.
There is some improvement in cohesive strength of the adhesive layer on addition
of silica. It also acts as a rheological modifier, enhancing the flow properties of the
adhesive and thereby properly filling of the cavities of the mechanically abraded
metal surface.

f. Effect of sulphur on shear/peel strength

[.,..,_.,.~,..~\-_--. . ,.......»t...~.~.--~,.~,.~»~~---...._._ M M

Sulphur (phr)

-o- Shear strength Al-AI (MP2!) -0- Peel strength Al-Al(N/mm)

Fig. 3.15 Effect of sulphur on Al-Al bonding. Resin with P: F

ratio 1: 2.9, CNSL: P ratio 1:1 and resin content 45 phr was used.

Fig. 3.15 shows the variation of shear strength and peel strength of Al-Al
bonds with sulphur content. Low amounts of sulphur improve the shear strength of
the adhesives initially. Sulphur may act as a weak adhesion promoter in this
concentration range. A minimal amount of crosslinking may be responsible for
this. But beyond this point there is a general deterioration of properties. The
adhesion promoter quality of sulphur is not very evident in this case.
7Chapter
é 737 7—7 *7 — 7 7 ’ ‘? ? "7 ’ ’ ? ’ 7 _ _ " ‘ __€
v

3.3.2. Rubber-metal bonding

Butyl rubber and aluminium substrates were used for this study.

a. Shear strength
1. Effect of P: F ratio

ri ‘I
0. 14 ” “’° " ““ ' * ’ m ‘_‘—"' ' " ” _‘“*’"'*"'** * [ 1

0.12 l

§\
§i 0.1 3 =; —O— P:F 112.9

-—l—-P:F 121.7

0.02 M
0 20 40 60 80
0 _ u . _ __ _ .,..___ i _ _ ._ __ ,______.=_,
ti —-X-—-P3F1:1.1

Resin content (phr)

Fig. 3.16 Variation of shear strength of llR- Al bonds with resin

content. Resin with CNSL: P ratio 1:1 was used.

Fig. 3.16 shows the variation of shear strength IlR- Al bonds with resin
content of adhesive formulation. For all P: F ratios (l:l.l, l:l.7, 112.], 112.9) the
shear strength initially increases and reaches a maximum between 30 to 35 phr
resin. On addition of higher amounts of resin there is loss in shear strength. On
addition of more resin the cured adhesive becomes stiffer and its modulus increases
beyond the modulus of butyl rubber. An optimum modulus is reached between a
resin content of 30 to 35 phr. Higher fonnaldehyde content leads to higher
mechanical strength and higher methylol contents. Hence a ratio of l:2.9 between
phenol and formaldehyde gives the best shear strength values.
 W Development of QNSL fiased Adhesives?
T...
3 ,_ t"\ ’
b?'t.'..‘ I-i . '. __
2, E ffect of CNSL: P ratio of resin V ;.__ ' I

0.14 it . ----- -­
(514 (REF,

i A -»— CNSL/P 100/0 /

_, 5; —I—
l1 -><--
--1- CNSL/P
CNSL/P
CNSL/P 75/25
so/so
25/75 . 5 022
i "”' 58, cat” \
-x— CNSL/P 0/100 \
t ’-“£'*_'~'_§1.:/“a°¢a~
O 20 40 60 80
Resin content (phr)

Fig. 3.17 Variation of shear strength of lIR- Al bonds for different CNSL/P
ratios. Resin with P: F ratio ll: 2.9 was used.

Referring to Fig. 3.17 it is seen that the presence of CNSL leads to a steady
reduction of shear strength of IlR- Al bonds. But addition of CNSL up to 25%
causes only a very marginal reduction in shear strength. Steric hindrance due to
aliphatic side chain of CNSL can be the reason for reduction in shear strength.
Here again, maximum shear strength is observed at about 35%» resin content.
Replacement of 25% phenol with CNSL can be an attractive proposal.

b. Peel strength
I. Effect of P: F ratio of resin

Q_Q .5. .............................. .._ ........................ .-_ ......... ..-.._......W.............­

._ 0.8
0.7 T
l‘ W
—O—P:F
-—I— P:F1:2.9
1;2.3
—a— P:F 1;1.1 —)(-— P:F 111.1

0 20 40 60 80
___W_.. .,_. ____ ,i--?,.-.._.__.._-..i-__._._-.__»----.----.--¢-v----¢--­

Resin content (phr)

<

Fig. 3.18 Variation of peel strength IIR- Al bond for different P/F
§'~=y*§'§- s . - _ _ s _ _-.____o.___, _ _ p __

Fig. 3.18 is a plot of 180° peel strength of HR-Al substrates bonded with an
adhesive formulation containing CNSL-phenol-hexa copolymer and neoprene
mbber. Peel strength values are also not very high. Maximum values are reached
about 45% resin content. Higher formaldehyde content is found to improve the pee]
strength. Resin content beyond 45% is found to lower the peel strength.

2. Effect of CNSL: P ratio of resin

0.9?
~0.5
0.6 -2
vi
08“ jé ""‘~\ i
0-Y ~i /'—-I-—CNSL/P
--02-CNNSL/P 500/0
ll ’--A-— 75/25
U _. _.. _ CNSL/P 50/50
0.4 1? —-)(-— CNSL/P 25/75
— 0_3 lg -11-CNSL/P 0/100
0.2 g
0.1 H
l

0 20 40 60 80
0 l‘_n....._. ._ __. ,_.;_..,__.g__T, _ ______. . __.._..._ __ _ __ __ ;..,W_...

Resin content (phr)

Fig. 3.19 Variation of peel strength of IlR- Al bonds for different CNSL/P
ratios. Resin with P: F rati0= l:2.9 was used.

Peel strength of HR-Al bond as a function of resin content is shown in Fig.

3.19. About 45% resin content is seen to be optimum, although in the range 25­
45% the variation is not much. ln agreement with earlier observations pure phenol
gives the best results, although replacing it with up to 25% CNSL does not lower
the peel strength much.
 i, frI .'
¢, Effect Of coupling agent on shear! peel strength

l
Development of CN'SL Based Adhesives_

, _ __ .. . ............._..._..................__...r..._..........._....|
I

i O 0.5 1 1.5 2
I ‘ -W.-_4;;;$ e ~-I .9.‘
Coupling agent (phr)

—-0- Peel strength (N/mm) Al-HR -—I— Peel strength (N/mm) Al—SBR
—t-— Shear strength (MPA) Al-SBR -—>(— Shear strength (MPa) Al-HR

Fig. 3.20 Effect of coupling agent on R- M bonding. Resin with P: F ratio 1:

2.9, CNSL: P ratio 1:1 and resin content 45 phr was used.

Fig. 3.20 shows the effect of addition of a coupling agent to adhesive

formulation. The coupling agent used is 3- aminopropyl tiiethoxysilane. Only in
the case of peel strength ofAl- SBR bonds the coupling agent concentration shows
any influence on the adhesive properties. Al-SBR bonds show a high value of peel
strength on addition of l to l.75 phr of coupling agent. There is hardly any effect
on the shear properties of Al» SBR bonds. The addition of coupling agent depends
on the nature of the substrate and this particular coupling agent is found to work
well for improvement of peel strength of Al-SBR bonds but not shear strength. The
Coupling agent has no effect on the performance of Al-HR bonds.
Ch_apfer_3_ _ *_ g _ _ _ __ fl *_:_____ g v__ g

d. Effect of carbon black on shear/ peel strength

Effect of carbon black on R-M bonding

-1_55 ."m“m“ mtmumumnmittmiw.mHm“m"M“inm.m-w"mtm-m"mHm“"mhw"mvmhWtmuwumhmum“m“m"mum“m"w“m_m-w"mtrum. Minimum

git; as \»=\.
O24681012
0 : , ii in — :**J-fr‘; ;;V*.** 7 L747,-L7 ,1; ‘g*;,;;’f; : K <1; a

Carbon black content (phr)

-_¢-_ Pee: strength (N)“n1m)‘Al-IIRW Peel strength (N/nnm) 'A|-si3R"

-4-- Shear strength (MPa) Al-IIR ——>-<——- Shear strength (MPa) Al-SBR

Fig. 3.21 Effect of carbon black on R- M bonding. Resin with P: F ratio l: 2.9,
CNSL: P ratio 1:1 and resin content 45 phr was used.

Addition of carbon black is seen to improve somewhat the peel strength of

Al- llR and Al- SBR substrates. This effect is more marked in the case of SBR. An
optimum carbon black content of 6 to 8% is indicated. The improvement in
cohesive strength resulting from the presence of carbon black is responsible for
better peel strength. Carbon black tie up more rubber per unit weight of carbon
thereby enhancing cohesive forces (16). Beyond 8% peel strength decreases due to
decrease in molecular flexibility.

e. Effect of silica on shearl peel strength

Effect of silica on R-M bonding

o.a r +—* ***" oi‘ * Tl

1 "tuna. mhm“m"m.m“".mtm-."m“t"min““tm“mHm.w"H_"m“nHmtH_w-m.mHm_m"mHH“mHm“mt".N-““m“..

7 _77 7.-V: é ‘
01
0 2+
0.4

4 6" 8flea‘,
10 12
0 '_T._i_-...I._:_>..&.;;-’-..V.;-.--.:’_i.-2<_..._;i£..,_i..-.._;..-+._..._.§i._....I_._Tf__- ....

Silica conte nt (phr)

——0——Peel strength (N/m rn ) AI-HR —I—-Peel strength (N/mm)AI-SBR
——A—-—Shear strength (MPa) AI-IIR -—>-4-—$hear strength (MPa) Al-SBR

Fig. 3.22 Effect of silica on R- M bonding. Resin with P: F ratio 1: 2.9,

CNSL: P ratio 1:] and resin content 45 phr was used.
 il. liit;
p——
Development of CNSL Bnsed Adhesives

F
J ll
Addition of silica to the formulation for Al-SBR bonding shows

‘l IE
improvement in peel strength beyond 6% (Fig. 3.22). The effect on peel and shear

,~1
W ii
strength of Al- IIR bonds and shear strength of Al-SBR bonds is negligible.

1 r 2
f, Effect of sulphur on shear! peel strength

N
1 2 p _,___ .,._,,,,,__,________ ,....,.,.,,,_,,..._.....W._.-.........._._..._...............~.._.........Mu._... ........ -._._..,

.1
~a

‘i

ll

01234 Sulphur content (phr)

-0- Peel strength(N/mm) Al-IIR —I— Peel strength (N/mm) Al-SBR

Fig. 3.23 Effect of sulphur on R- M bonding. Resin with P: F ratio 1: 2.9,

CNSL: P ratio 1:1 and resin content 45 phr was used.

Varying amounts of sulphur were added to the formulation for bonding IIR
and SBR to A1. Sulphur is known to enhance adhesion between metallic (17) and
rubber substrates. Fig. 3.23 shows the variation in peel strength of rubber metal
specimens on adding progressively larger amounts of sulphur. There is not much
variation in bonding strength on addition of sulphur although slight improvement is
noticed in the case ofAl-SBR.

3.3.3 Rubber-rubber bonding

Butyl- butyl specimens were employed for most of the experiments. The rest
of the experiments were on SBR-SBR specimens.

8. Shear strength
I. Effect of P: F ratio ofresin
Chapter 3 _ _.,

E
(U
Q.

-C
-0-I
U7
C
Q)
‘­
-4-I
0.07
/-\ 0.06

LI 0.05
0.04
0.03
pi pt ..
51 -—I--PIP 112.3
I

i.
H
\

* -0-— PIF 132.9

—-t——P:F1:1.7
U] 1.

L_
0.02 r: —)(—P;F 1:1.1
0.01
L

0
0 20 40 60 80
Resin content (phr)

Fig. 3.24 Variation of shear strength of IlR- [IR bonds for different P/ F
ratios. CNSL: P rati0= 1:1

Fig. 3.24 is a plot of change in shear strength with resin content for
butyl/butyl substrates. Here again a P: F ratio 1: 2.9 gives the best results.
Optimum resin content appears to occur at about 30 to 35 phr. The shear strength
values attained for [IR-IIR bonding are not high. Comparing the results obtained
for Al-Al bonding (Section 3.10. l) the performance ofthese adhesive fomiulation
for llR-A1 bonding and HR-IIR bonding is not satisfactory.

2. Effect of CNSL: P ratio of resin

0.07 y--I-—.—.._7 +~::-_-4.1.-..—_-fi__—~ -+:_~ —_—:;;.'.='-_- -—---._~-<>»~-..._-.--»<>¢-we----..-..~.».~_~.~-‘I;

~2 0.06
E 0.05

1 it
Z —O—- CNSL/P 100/0
Q-v
0.04 1 2 -0- CNSL/P rs/25
11L
I

0.03 ——a— CNSL/P so/50

-x— CNSL/P 25/rs
L
I5
0.02
0.01
1 -x— CNSL/P 0/100
'4' _. .___.. . . ___. .. __..i;
0
0 20 40 60 80
Resin content (phr)

Fig. 3.25 Variation of shear strength IIR- IIR bonds for different
CNSL/P ratios. P: F ratio 1: 2.9.
Fig. 3.25 shows the variation of shear strength of butyl — butyl bonds with
resin content. Each curve correponds to One ratio Of CNSL/P~ A5 in the Earlier (‘nap
 Development of CNSL Based Adhesives

pure phenol gives the best properties. But replacement of phenol up to 25 phr with
CNSL is seen to affect the performance very little. An optimum shear strength
occurs at around 35 phr resin content.
b. Peel strength
1. Effect of P: F ratio of resin

5%
0.7 1' l
?‘'
0 8 ........... ...... ._. ................. ......--.._.s....M. ......................... .... ..... ..~..-.....t.,

9-6 —O-P:F1:2.9
A it
H i;
Z
0-5 ii —I—P:F1:2.3 ii -—-A—P:F 111.7
—)(-—P§F 111.1

0 20 40 60 80
Resin content (phr)

Fig. 3.26 Variation of peel strength llR- llR bond for different P/F ratios.
Resin with CNSL: P ratio 1:1 was used.

Fig. 3.26 shows the variation in peel strength of IIR-llR bonds with resin
content of the fonnulation. Each graph corresponds to a different P: F ratio. The
higher the formaldehyde content the better the peel strength. In the range of 35 to
55% for most cases the peel strength is not very sensitive to resin content.
Chapter 3

2. E ffect of CNSL: P ratio of resin

_ t it -+- CNSL/P 100-/bi

;liY--I—
—-5-CNSL/P
CNSL/P 75/25
50/50
O-I i —)(— CNSL/P 25/75
0-—
‘ --X---CNSL/P O/100

O 20 40 60 80
Resin content (phr)

Fig. 3.27 Variation of peel strength llR- llR bond for different CNSL/P ratios.
Resin with P: F ratio l:2.9 was used.

The variation of peel strength of butyl- butyl bonds with resin content is
shown in Fig. 3.27 where each curve represents a different CNSL/P ratio. Although
pure phenol gives the best results partial replacement with CNSL upto 25% appears
to be a viable altemative. Peel strength is found to reduce with increase of resin
content beyond 45%. Higher resin content leads to higher modulus and presumably
too high a modulus for ILR-IlR bonding.
b. Effect of coupling agent on shear/ peel strength

_ # fit —O1
Bfe ct of coupling agent on R-R bonding

_% _; +
0 0.5 1 1.5 2
_i'_A____..t_.._._‘__. ..... ALJ. ‘_A

Coupling agent (phr)

-4- Peel strength (N/mm)) IIR-IIR —I— Peel strength (N/mm) SBR-SBR
+ Shear strength (MPa) IIR-IIR

Fig. 3.28 Effect of coupling agent on R- R bonding. Resin with P: F

ratio 1:2.9, CNSL: P ratio 1:1 and resin content 45 Phr was used.
 Development of CNSL Based Adhesives

Fi g. 3.28 shows the effect of varying amounts of coupling agent on shear and
peel strength of butyl-butyl substrates. There is only a small improvement in shear
and peel strength. The effect on SBR-SBR bonds is also negligible. The coupling

iQ‘
agent works well only with metallic substrates.
d. Effect of carbon black on shearl peel strength

Effect of carbon black on R-R bonding

as *_*_ fig.
3,
1 ___ _ ___,_,_,,~,,_...____,.,,,,,\,~,,.......___,.,_,.~,,,~.... ..,...~.,..-...._.,..... _ _~ .,..,-,~ -_. ...~-....-,~,-.-.._.....~..~.»- - -­

i
0 2 4 6 8 10 12 Carbon black content (phr)
-¢- Peel strength (N/mm) IIR-HR -_ Peelstrength (N/mm) SBR-SBR
-—A— Shear strength (MPa) IIR-HR

Fig. 3.29 Effect of carbon black on R- R bonding. Resin with P: F

ratio I: 2.9, CNSL: P ratio 1:1 and resin content 45 phr was used.
Fig. 3.29 shows the effect of carbon black on butyl-butyl bonding. At about
4 phr carbon black content, peel strength of both HR-IIR and SBR-SBR specimens
shows the maximum improvement, though moderate. Shear strength of HR-HR
specimens, on the other hand, does not show any improvement on addition of
carbon black. This is in agreement with observations made in Section 3.10.2 on the
effect of carbon black on the peel strength ofllR-Al bonds.

Carbon black generates a unique three-dimensional visco- elastic network

which produces a partial immobilization of the chain segments of the polymer and
improves the strength of the elastomer. Increasing the carbon black loading serves
to make additional carbon black surface available for rubber attachments and
improves the peel strength up to 4phr. Further addition of carbon black decreases
the peel strength. The reduction in strength may be due to agglomeration of the
carbon black aggregates to a domain that acts like a foreign body or due to the
physical contact between adjacent aggregates (18)­
? ._ 7 7 ? 7 _ _ _ 7 ~* ? 7 -7 — 7 — 7 7 ’ _i_ 4* — _
Chapter 3

e. Effect of silica on shearl peel strength

Effect of silica on R-R bonding

1.2
1.

O 2 4Silica
6 content
8 10 12
Q :_..t._...:..=£...;..i_i__-Ie__.:_..;_.._£_. _...__:_.e!..e__r_.... ._.A....__.. . _.. __­

(phr) ­
:'““—§—;.Peel_'streri'<;.]th (N/mm) IIR-HR --_ Peel strength (N/mm) sen-sen
—-.n—- Shear strength (MPa) HR-IIR

Fig. 3.30 Effect of silica on R- R bonding. Resin with P: F

ratio 1: 2.9, CNSL: P ratio 1:1 and resin content 45 phr was used.

Fig. 3.30 shows the effect of silica content on IIR-IIR and SBR-SBR
specimens. SBR-SBR specimens show improvement in peel strength from 4 phr
onwards. Substantial improvement is noticed at 8 phr which remains constant on
addition of more silica. Shear strength of HR-HR specimens does not improve on
addition of silica.

f. Effect of sulphur on shear/ peel strength

-------w-_----‘_...\\..-_..»-..-.~_.-w-~.--.-~.---- ........ t__... ........ -._ ........... we-.-..-.. ..... \»_.. ........ .-‘_.. ................ ----_.-v...i­

.::_..—_*‘;.._;._—_:&i.e.:;:‘....;.r_._
Sulphur content (phr)

-0- Peel strength (N/mn) IIR-NR —-I— Peel strength'i('N/mn) SBR-SBR

-5- Shear strength (MPa) IIR-IIR

Fig. 3.31 Effect of sulphur on rubber- rubber bonding. Resin with P: F

ratio 1: 2.9, CNSL: P ratio 1:1 and resin content 45 phr was used,
-f mi _' Development of CNS]. Based Adhesives

Fi g. 3.31 shows the variation in shear,’ peel strength of rubber specimens on

adding progressively larger amounts of sulphur. A marginal improvement in
adhesive formulation is observed in the case of peel strength of IIR-HR and SBR­
SBR bonds. Chemical interaction between sulphur and the rubber substrates can be
the underlying reason. Shear properties of IIR-IIR bonds, however, do not show
any improvement.

Table 3.3 shows the optimum values of coupling agent, carbon black, silica and
sulphur for M-M bonding, R-M bonding and R-R bonding.

TABLE 3.3

Optimum values of coupling agent, carbon black, silica and sulphur for M-M
bonding, R-M bonding and R-R bonding. (Resin with P: F ratio l:2.9, CNSL:P

|—* e I '*ratio" 1:1‘ and

" M‘resin content 45 phr was used)
~ — " " it " —‘- ‘ ‘ r
lvalue " 5' ‘r r
Optimum A Al-Al bonding 3 Al-SBR bonding ‘ R-R bonding

; Shear Peel Peel strength (N/mm) up Pecl strength (N/mm) IA

rp
4 strength strength 5 l 2.- H __­
“MP” l »B-BR 51 -IR
' IRI4i
agent i i
’(N/mm)

; black up 5 Q
4 ’SRS
T‘ Coupling 1.5 phr ’ l.5 phr l.75phr ‘ 1.25 phr l phr I

A Carbon A 4 phr A 4 phr 8 phr 4 phr \ 4 phr

ll 3 ' . " ~~ ‘ we ‘ -V ‘ I I ' I i—
we
silica 4phr__
‘T .[ - . _.__ _
3‘ Decreases 8 phrH
_.1 8 phrlA .
I . . .2
8 phr
_Sulphur 1 phr J l.5 phr 1 phr 2.5 phr ‘ 2.5 phr
7Chapter
—3 — — 7 — 7 ~ — 7 7 7 7 7 7 -—q
3.4 CONCLUSIONS

Judging from the bonding studies on Al-Al specimens a cure time of 2.5
hours and a cure temperature 140°C are found to give the best results for an
adhesive formulation consisting of neoprene and CNSL-phenol-hexa copolymer. A
resin content of 45- 55 phr at a P: F ratio of l: 2.9 gives the best overall properties_
Addition of 3- aminopropyl triethoxy silane improves the shear strength and peel
strength of adhesives used in metal-to-metal bonding considerably. Although
phenol alone gives the best shear and peel strengths, replacement of phenol with
25% CNSL for resin synthesis gives an almost equivalent performance.

Peel and shear strength values obtained for HR-Al bonding are not very high.
However, the best peel strength is obtained when 45 phr resin of P: F ratio l:2.9 and
CNSL: P ratio lzl is added to the formulation. The same resin when added at the rate
of 35 phr gives maximum shear strength. Addition of coupling agent is seen to give
higher peel strength in the case of SBR-Al bonds only. Addition of HAF carbon
black up to 8 phr improves the peel strength of SBR-Al bonds. Addition of 6-8 phr
silica improves the peel strength of Al-SBR bonds

For llR-HR bonds, similarly, 35-45 phr resin of P: F ratio I: 2.9 gives the
highest shear and peel strengths. In this case also, 25% phenol can be replaced with
CNSL with very little loss in properties. Addition of coupling agent has no
substantial effect on the shear / peel strength of SBR-SBR and IIR-[IR bonds.
Carbon black improves the peel strength in these cases marginally upto a maximum
of 4 phr. Silica enhances the peel strength of SBR-SBR bonds marginally. Sulphur
also improves the peel strength of SBR-SBR bonds to a moderate extent.

The peel and shear values reached indicate that this adhesive system is better
suited for Al-Al bonding than either of HR-Al or llR-llR bonding.

REFERENCES
l. J. Shields, Adhesive Hand book, 2"“ edition, Newnet Butterworth, London (1976)
2. 1. Skiest, 2"" edition, Van Nostrand Reinhold, New York (1977).
3. A.K.W. Scheib, Chemistry and Application of Phenolic Resins, Springer­
\/erlag, Berlin Heidelberg (1977).
._­
Development of NSL Based Adhesives

4 Encyclopedia of Polymer Science and Technology, Vol l, Wiley lnterscienee

publications, John Wiley & Sons, lnc., New York, 556 (l985)
5 ASTM D 3 I 88-00
6 ASTM D 3185-99
7 ASTM D 2656-79
8 ASTM D 903-98 (2004)
9 ASTM D 1002-49 (1981)
l0. H.Kollek, Int.J. Adhesion and Adhesives, 5, 75 (1985)
ll W.H. Weinberg, J.Vac. Sci. Technol., l l, 262 (1979)
12 B.G. Crowther, Rapra Review Reports, 8(3), 6 (1996)
13 A.J Kinloch, Adhesion and Adhesives, PP l56-157, Chapman and Hall, New
York (1981).
l4 J.A. Brydson, Plastic Materials, Butterworth-lleinmann Ltd., 7"‘ edition,
London, 128 (1999).
I5 G.F Morton and G.B Quinton i11 Rubber Technology and Manufacture, C.M
Blow and Hepburn (eds), P 467, Butterwoiths, London (1977)
l6 M.Kardan, Carbon black reinforcement of adhesives and sealants, paper
presented at the Adhesive and Sealant Council, Spring Convention, Las Vegas,
April (2000)
17 C.P.J. van der Aar, L.van der Does, J.W.M. Noordemeer and A. Bantger,
Progress in Rubber and Plastic Tech., Vol I6, No 2, 87-l 15 (2000)
18 B.B. Boonstran in: Rubber Technology, Van Nostrand Reinhold, New York
(I973)
Chapter 4
AGEING STUDIES ON RUBBERS MODIFIED
BY CNSL-PHENOL- HEXA RESIN

4.1 INTRODUCTION
4.2 COMPOUNDING AND CURING OF ELASTOMERS
4.2.1 Materials
a. Elastomers
b. Compounding ingredients
c. Solvents
4.3 COMPOUNDING OF RUBBERS BY TWO ROLL MILLING
a. NBR
b. SBR
c. IIR
d. CR
e. EPDM
f. NR
4.4 DETERMINATION OF CURE CIIARACTERISTICS
4.5 MOULDING AND SAMPLE PREPARATION
4.6 AGEING STUDIES
4.7 TESTING
a. Tensile strength, elongation at break and modulus
b. Tear strength
c. Miscellaneous tests
l. Compression tests.
2. Durometer hardness
3. Abrasion resistance
4. Swelling index
5. Density
6. Acetone soluble matter
7. Toluene soluble matter
C'1“P£"§___S _ _:::._,____:_. _ _j
4.8 REACTION OF PHENOLIC RESIN WITH ELASTOMERS
4.9 RESULTS AND DISCUSSION
4.9.1 NBR- Effect of resin on the ageing properties of vulcanizates.
a. Resin content
b. P: F ratio of resin
c. CNSL: P ratio of resin
4.9.2 SBR — Effect of resin on the ageing properties ofvulcanizates
a. CNSL content.
b. Resin content
c. P: F ratio of resin
4.9.3 Effect of resin content on the ageing properties of miscellaneous
rubbers
a. IIR
b. CR
c. EPDM
d. NR
4.10 CONCLUSIONS
REFERENCES
 Ageing Studies on Rubbers Modified By CNSL-Phen0l- Hexa Resin

AGEING STUDIES ON RUBBERS MODIFIED BY

CNSL-PHENOL- HEXA RESIN

4.1. INTRODUCTION

The linear molecules of a rubber need to be be crosslinked into a network to

get the desired physical properties in the final product. The crosslinking agents
generally used are sulfur and various accelerators, metal oxides, multifunctional
compounds, peroxides etc, depending on the nature of the rubber. During
crosslinking the rubber passes from a predominantly plastic state to a
predominantly elastic one because of the formation of intermolecular bridges.

The mechanical properties of crosslinked rubber undergo a marked change

on heating with deterioration in elasticity and strength. The behaviour of rubber
when exposed to high temperatures is strongly influenced by the presence or
absence of oxygen. More than half of the total change observed on ageing can be
attributed to oxidation processes (1). Reaction with oxygen causes chain scission
and /or crosslinking. After oxidation a vulcanizate sofiens or stiffens depending on
whether chain scission or crosslinking is more extensive (2-10).

Crosslink shortening with additional crossslink formation, crosslink

destruction along with main chain modification and cyclic sulfide formation, S-S
bond interchanges and degradation of the rubber backbone occur during ageing
(l l). These are due to post curing phenomena in which free sulfur is used up in
forming new crosslinks and the destruction of the weakest polysulfidic linkages.

The phenomenon of reversion or deterioration of properties, in sulfur based

cure systems is due to the decomposition of polysulfidic crosslinks (l2-15). This
leads to a reduction in crosslink density and consequently a loss of mechanical
properties. The chemical changes associated with reversion result in crosslink
shortening and crosslink destruction.

Since reversion due to ageing is an undesirable feature of vulcanizates,

various compounding methods have been developed to minimize it. There are three
possible approaches to this problem. I The established and best-known method to
minimize reversion is the efficient cure system. These vulcanization systems
reduce reversion by diminishing polysulfidic crosslinks and generating mono and

ll5
§ha2w;4 ._ _ __ __ _ __
disulfidic crosslinks in the networks (16). This approach is effective when lowering
the sulfur levels does not negatively influence other desirable properties like
fatigue, flexural properties, hysteresis etc. ll Another solution to counteract
reversion is to compensate for the loss of erosslink density and reduce main chain
modifications by adding a reactive chemical to the rubber compound to produce
thermally stable C-C crosslinks. This allows rubber compounds to operate under
more severe service conditions (17). III The loss in physical properties of sulfur
cured vulcanizates can also be controlled by adding age resistors that are capable of
reacting with the agents causing deterioration of elastomers. Thus the service life
of sulfur cured vulcanizates at elevated temperature can be increased by using
phenol- formaldehyde resins. These resins can give very thermally stable crosslinks
and the vulcanizates are immune to reversion at higher use temperatures (18-20).

In this study, the effect of varying the resin content, CNSL: P ratio
(CNSL/P — 100/0, 75/25, 50/50, 25/75, 0/I00) and total phenol: formaldehyde ratio
(P: F — l: 2.9,l:2.3,l:l.7, 1:I.I) of the resin was studied by incorporating the resin
into rubber vulcanizates and testing the properties of the vulcanizates before and
after ageing for l to l0 days at 100°C in an air oven.

4.2. COMPOUNDING AND CURING OF ELASTOMERS

A number of elastomers were subjected to study. These included

Acrylonitrile- Butadiene Rubber (NBR), Styrene-Butadiene Rubber (SBR 1502),
Isobutylene-lsoprene Rubber (IIR), Chloroprene (CR), Ethylene Propylene Rubber
(EPDM) and Natural Rubber (NR).

4.2.] Materials
a. Elastomers
1. Acryl0nitrile- Butadiene Rubber (NBR) was obtained from Apar Polymers
Limited, India. The sample used was grade N 553 with 33% aciylonitrile
content and having Mooney viscosity ML (l+4) at 100°C of 45.
2. Styrene-Acrylonitrile Rubber (SBR 1502) was obtained from Japan
Synthetic Rubbers Co.Ltd., Tokyo.
Specifications of SBR
-_— , Ageing Studies on Rubbers Modified ”ByCN 5L~Pf"-’"01', flex" B955?!

Volatile matter, % mass - 0-23

Ash, % mass - 0-24
Organic acid - 5.53%
Bound styrene - 24.3
3, lsobutylene-Isoprene Rubber (llR) was supplied by Bayer Polymers, India.
4. Chloroprene (CR W) was supplied by DuPont, Akron, Ohio.
0
Mooney viscosity ML (l+4) at l00 C - 47
5 Ethylene Propylene Rubber (EPDM) was supplied by Zenith Rubber and
Plastic Works, Mumbai.
6. Natural Rubber (NR) — ISNR- 5 was supplied by the Rubber Research
Institute oflndia, Koltayam, Kerala. Specifications of ISN R-5 is given below.
Mooney viscosity ML (l+4) at 100°C — 82
Dirt content, % by mass, max — 0-05
Volatile matter, % by mass, max — l
Nitrogen, % by mass, max — 0.7
Ash, % by mass, max — 0.6
Initial plasticity, min — 30
Plasticity retention index — 60
b. Compounding ingredients
I. Zinc Oxide (acivator) was supplied by M/s Meta Zinc Limited, Bombay. It
had the following specifications.
Specific gavity — 5.5
ZnO content — 98%
Acidity —- 0.4%
Heat loss, max (2hrs at 100°C) — 0.5%
2. Stearic acid (co-activator) used in the study was supplied by Godrej Soaps
(Pvt) Ltd, Bombay and had the following specifications.
Specific gravity _ 0.85 1 0.01
 _ f ._ i 7 7 i i i j _ V
Chapter 4

Melting point » 50-69°C

Acidnumber -— 185-210
lodine number — 9.5
Ash content — 0.1%
3. Sulphur was supplied by Standard Chemical Company (Pvt) Ltd, Chennai.
The sample used had the following specifications
Specific gravity — 2.05
Acidity —- 0.01% max
Ash — 0.015 max
Solubilityin CS2 —— 98%
4. Tetramethylthinram disulphide (TMT D) - It was supplied by Flexys,
Netherlands. It had the following specifications
Melting point - 108°C
Moisture content - 0.12%
Ash - 0.03%
5. Mcrcaptobenzothiazol disulphide (MBTS)
MBT S was supplied by Bayer Chemicals, Bombay. It had a melting point of
t
165°C and specific gravity- 1.34
6.. Ethylene thiourea (NA 22)
NA 22 was commercial grade supplied by Standard Chemical Company (Pvt)
Ltd., Chennai. It hadthe following specifications
Specific gravity —- 2.05
Acidity — 0.01% max
Ash — 0.01% max
Solubility in CS2 — 98%
7. Magnesium Oxide (MgO) was supplied by Fine Chemicals Ltd., Mumbai_
Specifications
Water soluble matter - 25
-_— . ____ _ _ . H Ageing Studies on Rubbers 1\40d_1fi'ed By CNSL-P181103‘ Hex" R95???

Loss in ignition at 100°C - 8%

Chloride - 0. 1%
Sulphate - 0.5%
Arsenic - 0.000 I %
Iron - 0- I °/0
Lead - 0.002%
8. Octylated diphenylamine was supplied by Y:-isho Industries Ltd., Mucmbai,
India.

9. Styrenatcd Phenol (SP) was supplied by Olympic Chemicals, Maharashtra,

India.

1.0. Precipitated silica used was of commercial grade supplied by Sameera

Chemicals, Kottayam. The specifications are given below
PH (5% aqueous solution) - 6.3
Specific gravity - 2.03
SiO2 on dried sample - 90%
Loss-on heating (l05"'C) - 5.5%
ll. Carbon black (IIAF N330) was obtained from Philip Carbon Black Limited,
Kochi, India. It had the following specification
Appearance - black granules
DBP absorption - I02 cc/100g
Pour density - 376 kg/m3
Iodine number - 82
12. Dicthylene glycol (DEG) was supplied by E. Merk Limited, India.
13. Dioctyl phthalate (DOP) was supplied by Vensbar Chemicals (P) Ltd, India
and had the following specifications
Specific gravity - ()_98
Viscosity (cp) _ 60
5-‘heviers __sst_s
14. Aromatic oil was supplied by Hindustan Petroleum Corporation. It had the
following specifications
Specific gravity - 0.95 -0.98
Viscosity gravity constant (VGC) - 0.907
Aniline point - 38°C
15. Naphthenic oil was supplied by Indian Oil Corporation. It had the following
specifications
Colour — light
Pour point - 20
Aniline point ~ 78°C
Viscosity gravity constant -— 0.85-0.9
Aromaticity - 10
16. Paraffinic oil was supplied by M/s Hindustan Petroleum Limited, India. It had
the following specifications
Viscosity gravity constant — 0.85
Aniline point ~ 96%:
c. Solvents

1. Toluene was supplied by Fine Chemicals Ltd., Mumbai.

Specifications
Boiling range - 950
Acidity - 0.012
Alkalinity - 0.012
Non volatile matter - 0.002%
2. Acetone (AR) grade was supplied by Quali gens Fine Chemicals. It had the
following specifications
Minimum assay - 995%
W;/ml at 20°C - 0.789-0.791
Refractive index - I-35' I-36
 _ Ageing Studies on Rubbers Modified By CN$l.-Phenol- Hexa Resin

4.3 COM POUN DING OF RUBBERS BY TWO ROLL MILLING

Mixing and homogenization of elastomers and compounding ingredients

were done on a laboratory size two roll mill. The two roll mill used has rolls of 150
mm diameter and 320 mm length. The mill is equipped with retaining guides, with
a distance between the guides at the nip of 250 to 280 mm. The ratio between slow
roll and fast roll is 1: 1.25. The clearance between the rolls is adjustable from 0.2 to
8 mm as a minimum range of adjustment.

The mixing was done according to ASTM standards. Rubber was masticated
on a cold mill and the compounding ingredients were then incorporated. Resin was
added along with the filler. Resin content was varied from 0 to 25 phr. Resins with
different phenol: CNSL ratios (CNSL/P — 100/0, 75/25, 50/50, 25/75 and 0/100)
and total phenol: formaldehyde ratios (P: F — 1: 2.9, 1:2.3, l:l.7 and 1:1.1) were
incorporated into the rubber.

a. NBR

NBR is a copolymer of acrylonitrile and butadiene. Structural formula of NBR is

CH2 on cu CH2 CH2 CH

cu

NBR is less permeable to gases and have good oil resistance. Due to polarity NBR
vulcanizates have higher electrical conductivity.

It was initially compounded using Formulation I which employs a

combination of three fillers. As this fonnulation was difficult to mix subsequently
Formulation ll which employs only silica tiller was employed. Figs 4.1- 4.13 are
based on Formulation l and Figs 4. 14- 4.23 are based on Formulation ll.

NBR was compounded as per ASTM D 3187-00 (2004) (21).

 f3{'"E*€'§ 11 _ 1 1 __ _____1 _ ,_1________15_ K _ ,1 ____

Table 4.]
Formulation I used for NBR mixing

h;:5::1__2_
V

R0 1 A“R5 A3 ;~
L_ R10 R15 2 R20 R25“
H

"‘fim“Ji
1

N BR

2A 0.22 0.2
2
i000; I *0 T00 J "0 ‘100 ~11

j414I4
‘100
\

f 7 Z100 7 7 \

ZnO 4
2
4
2
1
M 42
1 Stearic acid
WS 1.5
1
W
1.5 1 1.5
W

1 1.5 1 1.5 “ 1.5

H

‘\

TMTD 0.2 0.2 ~, 0.2 11 0.2 ‘~ H

MBTS I 1 .; 1
50 as
M
~ 501“
“~ 1H;é
50 0 1
50
Silica 50 50
1 1 \
\

1* 50
\
\

Clay 50 50 50
50 i 5 5 ““50
50 A
, 501 5
U
U
\

C3CO3 ‘L

50 50 \

"7"2 22 2" 22
‘\
\

DOP \

\
U
‘a

~ 25
DEG \

\
\

1
U

\ U

1 SP

15K 55
U
M
M

Cl resin \
X

Resin
:i;;;;;iA_-.451; \

\
\

4_b1__52_ ,_2,2*______:
Table 4.2
F ormulation ll used for NBR mixin 8
0” 0”*f77li0” i150 V1110 _T*_ ______
;_7‘__ms‘
4477i;t'1i21r1» R25
???__[
71

0 100 l 100 1 100 [0100

‘f 42N24 24
1

NBR ‘L

\
100‘ 1 \
T00
42
i

ZnO U

‘1
41 \
1

\
4 M

:~ 2
Stearic acid
“11 0.2
1‘*iA
1 .51.5
1

2 2
S 1.5 \
1

1.5 1.5 1.5 ‘

1 "I M
1 1A10.2
\
1

0.2 *
0.2 \
1
\

TMT D \

0.2 ]* 0.2
MBTS 1 1

J 50 1 50 » 50 1 j 50
\

Silica 50 50
5"515 Ii\ 2X‘ 21‘ 2
N

15
“‘ 1!
1

DOP \
5 5 \

DEG 21 1
2 Q2 1

Resin , 0 1* 5 1 10 1 l5_J120 1 25 1
M
 *7 {lgeirtg Studies 0ngRubbers Modified By CN5LfPh£'*!Qi- Hex? Resig

b. SBR

SBR consists of about 25% styrene, with butadiene making up the remainder.

CH2 cu CH CH2 CH2 CH

C6H5

Heat resistance of SBR is better but low temperature flexibility and tensile strength
are less than for natural rubber. Its vulcanizates are poor conductors ofelectricity.

SBR was compounded as per ASTM D 3 I85 ~99 (22). ln the case of SBR an
additional study was conducted to investigate the effect of directly adding CNSL to
the formulation instead of the resin. This formulation is given in Table 4.3. The
effect ofaddition ofthe resin was studied using the fonnulation given in Table 4.4

l
_. .,.0.. .\_. _u.
_. __fi __. Ii._
Table 4.3
Formulation used for SBR for mixing CNSL directly

C0_[C5C]0Cl5C20_LC25.
ZnO
SBR
l4l4l4i4‘4l4*
Stearicacid 2.2*2 2i2i2.
I00 A 100 8 100 l I00 l 100 100

l
S 2 . Z 2 4 2 ~ 2 8 2 ll
TMTD 0 0.2 4 0.2 0.2 0.2 ' 0.2 0.2 3
MBTS T 0.8 0.8 T 0.8 . 0.8 0.8 0.8 t
Carbon black . 50 50 ‘ 50 50 0 s0 s0 1

Aromatic oil 1 5 . 5 T 5 * 5 2 5s
i_
|
CNSL 0 s@10 1s202sg
 §h9P£@'_4,, _ _________,__sc is
Table 4.4

. R0gR R20t51%
Formulation used for SBR for mixing resin

ii ‘E
7Z:‘:Z7 ‘0

t \\\\
0 7; ‘Roll
7 i l ,F’ (R05
* _ [ iiit‘i 7' 15’ 7
5* * *5 5* "tr *F5*:*t* R251“
t

t
‘t

\ \ é—
ZnO 4t4t444t
SBR \ 100 ‘ 100 ‘ 100 t 100 t 100 M 100 “
2L22\22
sTMTD2‘2222
it

Stearic acid

it

it

it
3 0.2 At0.2

c. llR
‘i tt
\ ‘ ‘' 50
it0t~10
tt
0.2 7 \ ti‘
t‘
, it
\1itt50
0.2 0.2
‘t ‘t ‘i
t *“it
MBTS A 0.8 ,5 0.8 t 0.8 t 0.8 M 0.8 A 0.8 “
Carbon black t 50 y 50 3 50 H 50 x
\

Aromatic oil i 5 2. 5 , 5 2; 5 , 5 ~. 5 t
Resin ‘t_t__:;:tt;:_,;€;{%:,;_t:T:1J:’___LL,jjit
5 M 15 tA 20 \ 25
0.2 it

CH3

c|—t2 c CH CH2 CH2 c

CH3 CH3 D

HR consists ofisobutene with a minor part of isoprene.

IIR has excellent impermeability to gases, outstanding dielectric properties,
good resistance to tearing, good ageing properties at elevated temperatures and
good chemical stability. They also resist weathering, sunlight, ozone, mineral
acids, oxygenated solvents, water absorption, animal and vegetable oils. Resistance
to flexing and abrasion is outstanding. llR was compounded as per ASTM D 3188­
00 (23)
 i Ageing Studies on RubbersM0dified?ByiCNSL§l?l1enol§ Hexa?Resin

Table 4.5
Formulation used for [IR
.-__
ii it T
R0_1-Rs
.4.R10
_ R15
_ 1 .__L5
in; 1 100 100 100 = 100
R20
100 "1R25
100
ZnO
Stearic acid
S
TMTD
0.5 1 0-5 i 0.5
i s0 ,50
5 1 511 S ‘
MBTS 0.5 0.5 0.5
50 r
i

Carbon black 50 50 S0 I
5.
Paraffinic oil
Resin '0 5 10
i, r— _ — — __ — _ —7-—_ __ _ l5
S 5
20 25 .
d. CR
Structure of CR is

c|
(-- CH2-CICH-CH2— ) H

CR has good mechanical strength, high ozone and weather resistance, good
ageing resistance, low flammability, good resistance towards chemicals, moderate
oil and fuel resistance and adhesion to many substrates. CR was compounded as
per ASTM D 3190-00 (24)
Table 4.6
Formulation used for CR
T

A R0 Rs R10 R15 H‘ R20 K R25 “

CR it i 0 0100 1000 100
14 44
100 100 it 100 t
4.
M g0
ZnO
Carbon black
s55
50“ 501. 50
4
s
50
4
5
50 50
5.
Naphthcnic oil
Ethlene thiourea
5 55
1 0.5 ~ 0.5 0.5
s
0.5
5
0.5
. 5 ‘u
0.5 A
Octylated diphenylaminc X‘ 1 1 11 1 11
20 1 1 I!
Resin 0 , s ii 10 15
at 25 -1
Fkantqi , _ _ i___s____p___i__i_i __2__ _ _ _2_

e. EPDM

In EPDM, ethylene and propylene monomers combined to form a chemically

saturated stable polymer backbone and a third conjugated diene monomer is
terpolymerized in a controlled manner to maintain a saturated backbone and place
the reactive unsaturation in a side chain available for vulcanization. The two most
widely used diene termonomer are ethylene norbornene and dicyclopentadiene.
*

CH2 CH2 CH2 (.:H diene

CH3
_.,__

EPDM polymer structure is

EPDM have excellent ageing resistance, ozone resistance, weather

resistance and resistance to chemicals. Colour retention in coloured compounds is
excellent. It exhibits good dielectric qualities and high heat resistance. Low
temperature properties are excellent. Resilience and tensile strength of EDDM
rubbers are low, and resistance to petroleum derivatives extremely poor. EPDM
was compounded as per ASTM D 3568-03 (25)

A 2
Table 4.7
Formulation used for EPDM
ii 2 24_ii_1i4_14_1i#1i4ii4__ f i i _ T _ : _ Li T: 11110

ZnO \
F????7???"'ii
\ F \
R0 L_______
l R5 1 R10 R15
m_m_R20 1 R25

A2
‘1

R4 *4»4»4i
EPDM t 100 1 100 , 100 1 100 ,~ i00 7‘ 100 A
Stearic acid I" 2 l 2 2 l 2 1 2 l
4l
s 1 1 1 1 1 1 ‘ 1 *1 1
H 1 ti ll ii 1­
TMTD 7‘ 0.5 l 0.5 ‘1 0.5 0.5 ~ 0.5 ;~ 0.5
MBTS T“ 2 1 2 1 2 \ 2 ~ 2 1
Carbon black 1 50 l 50 Q 50 ‘i 5° 50 1“ 50
Paraffinicoil l 5 ‘l
l 5 § 5 ,1
Resin A‘ 0 1 5 10 15 1 Z0 if5 5 .
i __ if i ,,_—— ,7‘; * 4 * 4— '77 ’7’7" i I l
5
25 :1
 Ageing Studies on Rubbers Modified By Cl\lSL-Phen0l- Hexa Resin

f. NR

The rubber hydrocarbon component of NR consists over 99.99% of linear cis

1,4 polyisoprene.

st
(_- CH2-C=CH-Cl—l2— )
Tl

Average molecular weight of polyisoprene in NR ranges from 200,000 to 400,000

with a relatively broad molecular weight distribution. Due to this broad molecular
weight distribution, NR has excellent processing behavior. NR has high tensile
strength, high rebound elasticity, good low temperature flexibility, excellent
dynamic properties, low heat build up and very good resistance to abrasion and
fatigue. Poor resistance to oil and ozone and fuels are the drawbacks.

NR was compounded as per ASTM D 3184 -89 (26)

Table 4.8
Formulation used for NR
~i‘ V * — —' '~ ~~ ——_u-u-—~-i ..
:7
R0 R5 A l R15
|

Ttiii
lNR 2 160 100 l 100 3
lZnO é 4 2 4 4 4
9 R10 R20
100
4
"Z1960
R25

2 Stearic
si TMTD acid
" 2.50.22.5 2
2.5 2 2 2
2.5
2
2.5
2
2.5
0.2 0.2 @ 0.2 0.2 0.2
l MBTS 0.8 0.8 0.8 0.8 0.8 0.8

Carbon black(HAF) \ 50 l 50 % 50 50 50 50
l Aromatic oil 5 5 I 5 5
LResin 0 5 I0 15 5
20
_-Q
5
25
§h"_P“’!4_ _ _ _ z ._ _ Z ..___-________ ___. - _ _ .

4.4 DETERMINATION OF CURE CHARACTERISTICS

Cure characteristics of the elastomers were determined on a Goettfert

Elastograph Model 67.85. It is a microprocessor controlled rotorless cure meter
with quick temperature control mechanism and well defined homogeneous
temperature distribution in the die. In this instrument a specimen of definite size is
kept in the lower half of the cavity which is then oscillated through a small
deformation angle (0.2°) at a frequency of 50 oscillations per minute. The torque is
measured on the lower oscillating disc half. The following data can be taken from
the torque - time curve.
a. Minimum torque M1, -Measure of the stiffness of the unvulcanized test
specimen. It is the torque shown by the mix at the test temperature before the
onset of cure.
b. Maximum torque M“ - Measure of the stiffness or shear modulus of the fully
vulcanized test specimen at the vulcanization temperature. It is the torque
recorded after curing ofthe mix is completed.
c. Scorch time (TlO)- Measure of the time at which vulcanization begins. It is
the time taken for attaining 10% of the maximum torque
d. Optimum cure time (T90) — Time taken for attaining 90% of the maximum
torque.
e. Cure rate index— Cure rate index is a measure of the rate of vulcanization
based on the difference between optimum vulcanization and incipient scorch
time. Cure rate index was determined from the following equation
CR1 = 100/ (T90-T10)

The Elastograph Microprocessor evaluates the vulcanization curve and prints

out the data afier each measurement. A typical cure rate curve for NBR is shown
below.
 Ageing Studies on Rubbers Modified By CNSL-PhenoI- Hexa Resin

1 0‘ n4. xii‘. ‘:.ii£t1.H‘ ;§¥'.'?3"1:‘*5"‘ T1‘

1‘r
Nm.
.3 ..-....... .._ ._ ....._....>.-._.-¢ii_.....-i_____¢_- -.-..-a -,-V - I'\ - -—­

.7? 4.»!

~Q‘ 1 %i__ — "

>

57 1‘.
‘I 1I

Ir 1

3* W ‘t
\t vi
_ _ _ 4-1­

.2‘ ‘F

10,7‘ '

0 6 5 12 I8 24 Hi n 31 ~-*,__ __._2,_- _ ._ ,_ _ _. _~:____ W ______?_ .

1

F ig.4.l Cure rate curve for NBR (Resin content 25 phr, P: F ratio l:2.9,
CNSL:P ratio 1:1)

Tables 4.9 to Table 4.16 show the cure characteristics of different rubber
formulations.

Table 4.9
Vulcanization characteristics of NBR for different resin contents

P:F Resin Vulcanization characteristics

ratio content Scorch time Optimum Minimum Maximum
(min ) cure time torque (N.m) torque (N.m)
(min )
1: 2.9 0 3.5 0.188 0.552
5 3.9 0.12 0.62
.10 4.2 0.11 0.43
015 5.6 0.13 0.311
20 8.5 0.11 0.321
25 12.4 0.027 0.3833

129
Chapter 4

Table 4.10
Vulcanization characteristics of NBR for different P: F ratios
Resin P:F Vulcanization characteristics
content ratio Scorch time Optimum Minimum Maximum
(min) cure time torque (N.m) torque (N.m)
(min )
25 112.9 1.8 12.4 0.027 0.3833
1:2.3 0.5 12.42 0.097 0.749
111.7 0.1 11.1 0.13 0.357
l:l.l 1.2 12.4 0.1084 0.5454

Table 4.11
Vulcanization characteristics of SBR for different CNSL contents

Scorch time Optimum Minimum Maximum

(min) cure time torque (N.m) torque (N.m)

l:2.9 05 1.2
3.8
(min )
12.1
19.5
0.112
0.1127
0.712
0.631
10 2.5 13.1 0.1933 0.6032
15 1.8 11.9 0.133 0.548
20 1.6 10.7 0.125 0.563
:25 1.1 13.9 0.123 0.592

Table 4.12
Vulcanization characteristics of SBR for different resin contents

P: F Resin Vulcanization characteristi cs

ratio content Scorch time Optimum Minimum Maximum
(min) cure time torque (N.m) torque (N.m)
l:2.9 05 1.2
1.4
(min)
12.]
13.4
0.112
0.12
0.712
0.61
10 1.5 14.2 0.13 0.54
15 1.1 13.2 0.12 0.61
20 1.3 14.5 0.11 0.59
25 1.6 15.2 0.12 0.512

130
 f Ageing Studies on Rubbers Modzfied By CNSL-P1?I8??I01?- H810 R8513!

Table 4.13
Vulcanization characteristics of SBR for different P: F ratios

TResin TP: 4 _ _ j Vulcanization characteristics

content *ratio A4 Scorch time ; Optimum Minimum \ Maximum
1 1 (min) curetime torque (N.m) 4 torque (N.m)
I125Hl:2.9 1.6 M
._. .. . . 0.12
115.2 ., 2 1___
I (min) .. _._
,0.s12
!1:2.3 Q 1.1 _13.2 é J 0.1406 10.6464 if 2
111.7 _11.5 94.1 0.1025 ? N 10,6406 ow
111.1 11.2 % % i0.1377 _ j 10.2792

Table 4.14
Vulcanization characteristics of CR for different resin contents

P: F Resin 6 _ jVulcanizationcharacteristics j _ __"

1: ratio content Scorch time Optimum 1 Minimum 4 Maximum
. " (min) cure time 1 torque (N.m_) 1 torque (N.m)
? 1 M 1? _ §_§1nin)_w
“ 112.9 0 0.20 YA
L94
_0.16?_ H % _
5 0.99
1. 0.12 if
12210 0§_16
. 10.3
.1l.l
_ __2
0.12
0.11
0.719
e 0.72.9
1

la 15 2 0.16m” 11.7 0.12 0.610

120*‘
_' 0.11 U 1 12,2
1
1

0.13 1 0.629
1 . 125 W120. _ 13.2 i
0.12 10.52
 — ? 7 '7 — 7 — >7 W’ * é 7 T _ _ _ _ ' —i
Chapter 4

Table 4.15
Vulcanization characteristics of EPDM for different resin contents

1 P: F 1 Resin? _ T qé _*\;/*uleaq_11i2ationghgrqcterigigsL _7__q__;

i­
‘1 ratio 1 content 1 Scorch time ‘A Optimum Minimum 1 Maximum
ii

1 (min) 1 cure time 1} torque (N.m) 1 torque (N.m)

H

1 _'11 __1»
s 5_’ ,-_f me1W120‘
(111111); J5L
1

__.
%l:2. i 2 214.24 ‘0.i1i i Z 276.2%‘ :2
__,_ i _:4 _' f _* _' —— : : i 1 7 1

1 I0-12 f J 14-545, 2 T4111/:2 5 5 _ lo-245

‘0.121i 2 2 M264 “'1
1 15 0.14 }_121.4q _ q _ _,0.111 ;0.2902 T
1 7262 f0.20 2 20 07154 _ 2 L0594 2 T
\

2 , I25 2_j0- 5 20-4 Z 210-132 ;0-194 2

_ :__, 5__1
“Ti

Table 4.16
Vulcanization characteristics of [IR for different resin contents

IPIF ‘Resin L f q W f _qq _ qVulcanizgtionqcliaracteqristiesf _

X‘ ratio \‘ content 7* Scorch time 1‘ Optimum V Minimum ‘I Maximum
,\ 1 K (min) 1 cure time 1 torque (N.m) torque (N.m)
2 2 41 2 2 use 2 _ I 229111") out 2 L 5 2 2 2 2 J - 2
l:2-9 ‘1 0 1 0.5 1 5.6 W 0.262 1‘ 0.4267 #1

__,

1
1 e1? e 113? 5 W9 5510.054; 5 10.6152
——¢——e——~——e——e1e~—* __

J o1°j1~i’> 51118 K Z 1;)-061 1 0611 2 _.. \

_ 1 _ 1-5; , _ 114 1°-05 2 Q20-541 1; 1

[1T20__ 1.65 1 13 0.03q _ _ L0-550
1154:
_ _ 1 ____ __ __ *1 1;T_*2 ‘T1.4‘2‘
T __ __1 __-‘ _70.06 it 7‘
1_ ~ oi‘ 0.452
_ :e_@ _,
51
J1
 ___.
Ageing Studies on Rubbers Modified By CNSL-Phgm) I- Hexa Resi"

Table 4.17
Vulcanization characteristics of NR for different resin contents
.7‘ — 4"- - ~ r " ' I ~ ~~-_-7 I 7,, 4 7 _—I-""'-F'-_'-.-—._i—'q
P; F Resin g g Vulcanization characteristics J/,,_.,-gt
ratio content I Scorch time 1 Optimum I’ Minimum I it Maximum 1
r

i1

g i , (min) W V g A
. A (min) i curetime L torque (N.m) i torque (N-In) 1
1;2.9 F0, g ‘0.3 g ,12, ,,i,,Q,.1_ 1.18 //i
.. 1 1 4--"""""'.'

is _10.4 ,14.3, g 10.21,, 0.946;,/,7

710 g 70.5 _12.4 0,132 K 1.11 ___,__,..;
15, g 0.6 _ 1.3 g_g _ 10.244 0.946;///J
g 09_,__,_._.__
E0 . 1-1. . 1.4-4 . . ;Q--15 -. ll-1,//—-r
‘ 25 1_1.2, 12.8 ,_ , 0.1914

4.5 MOULDING AND SAMPLE PREPARATION

Initially cure characteristics of the mixes were determined at l50"C on at

Goettfert Elastograph (Model 67.85). Vulcanization to optimum cure time was
then carried out in an electrically heated hydraulic press with 30 cm x 30 Cm
platens and 13.72 MPa at 150°C. Mouldings were cooled quickly in water at “"3
end of the curing cycle and stored in a cold and dark place for subsequent p11)’ Sical
testing. From the vulcanized sheets dumb-bell specimens and angular spficlmens
were punched out.

4.6 AGEING STUDIES

Oxidative ageing tests were carried out as per ASTM D573-88 (27)
procedure, using an oven at 100°C. Specimens were subjected to ageing for 1, '2> 3’
4, 5, 6 7, 8, 9 and 10 days. Physical properties of the specimens before and afier
ageing were determined afler 24 hours of conditioning at ambient temperaturfl
Clzapterfi g
_

4.7 TESTING
a. Tensile strength, elongation at break and modulus (AST M (D 412-98 a)
(28).

From the vulcanized sheet dumb-bell shaped specimens were punched and
were tested on a Zwick tensile testing machine. The crosshead speed was
maintained at 500 mm/minute.

b. Tear strength

This was carried out according to the standard ASTM D 624-00 (29) using
angular specimens punched out from compression moulded sheets. Throughout the
test the rate of the grip was kept at 500 mm/min.
c. Miscellaneous tests

l. Compression tests- ASTM D 395-03 (30) was used for the compression test.
Test specimens were compressed for 22 hours at 70°C in an air oven and the
final thickness was measured 30 minutes afier removal from the clamp.

2,. Durometer hardness — Hardness of the samples was measured by means of

Shore A Durometer according to ASTM D 676-86 (31)

3. Abrasion resistance- Abrasion resistance was measured using a DIN Abrader

as per DIN 53516 with a load of 5N. (32)

4. Swelling index- Swelling index was measured as per ASTM D 3616-95 (33).
0.5 g of the vulcanizate was kept in toluene for 20 hours. Samples were taken
out, quickly dried with a filter paper and the swollen weight was found. The
swollen samples were dried in a vacuum oven at 60°C for l2 hours and the
deswollen weight was noted.

Swelling index = (swollen weight- deswollen weight) /mass of dried gel

Gel % = mass of gel x 100/ initial weight
5. Densiry- density of the vulcanizate was determined according to ASTM D
297-93 (34)
 Ageing Studies 0" Rubbers Modified By CNSL-PheIl01- Hexa Resin

6. Acetone soluble matter- Acetone soluble matter was determined as per ASTM
D 297-93 (2002) (34). Approximately 2 gm of the sample was cut into strips
and extracted with acetone for 16 hours using extraction apparatus at 70°C and
then dried at 70°C for 2 hours.
Acetone soluble matter, % = gms of extract x lOO/gm of specimen.
7. Toluene soluble matter- was determined by extracting the sample with toluene
for 24 hours.
Toluene soluble matter = gms of extract x 100/ gm of specimen.

4.8 REACTION OF PHENOLIC RESIN WITH ELASTOMERS (35)

Three types of chemical reactions are possible during the curing of rubber in
the presence of phenolic resin - self-hardening of phenolic resin, crosslinking of
phenolic resin with rubber and vulcanization of rubber.

There are two possible mechanisms for resin cure of unsaturated rubbers-
The 'chroman mechanism' and 'allyl hydrogen mechanism'

(1) The chroman mechanism

a. Formation ofquinone methide

At high temperature water is eliminated from the resin leading to the formation of
a quinone methide.

OH OH 0
I OH
CH20H'~ R '
CH20 // CH2
-H2O
..-/ -: R' ....
,/
./
/
~//
~

~'. -s-:
R R -:>: /.".

R /~
...,/
R

Fig. 4.2 Formation of quinone intermediate

135
_ t _ __ s Ageing $*"4='@§ e'g1£'*2b§*iM2d*fi@4 By ¢N§k—Pl=e*9'-_"¢Ifl Ifiefil

6. Acetone soluble matter- Acetone soluble matter was determined as per AST M
D 297-93 (2002) (34). Approximately 2 gm of the sample was cut into strips
and extracted with acetone for 16 hours using extraction apparatus at 70°C and
then dried at 70°C for 2 hours.
Acetone soluble matter, % = grns of extract x l00/ gm of specimen.
7. Toluene soluble matter- was determined by extracting the sample with toluene
for 24 hours.
Toluene soluble matter = gms of extract x lO0/ gm of specimen.

4.8 REACTION OF PIIENOLIC RESIN VVITH ELASTOMERS (35)

Three types ofchemical reactions are possible during the curing of rubber in
the presence of phenolic resin - self-hardening of phenolic resin, crosslinking of
phenolic resin with rubber and vulcanization of rubber.

There are two possible mechanisms for resin cure of unsaturated rubbers­
The ‘chroman mechanism’ and ‘allyl hydrogen mechanism’

(1) The chroman mechanism

a. Formation Qfquinone n-iethide

At high temperature water is eliminated from the resin leading to the formation of

- /-I.
a quinone methide.

2_._ R‘
on
OH OH O
on OH

.R .__R l
. .CH,OH H20 C]-{2QH R. , CH2
R "R
)»

R:C1sH31 -l'\

R'= (‘ct-|2-) or (-CH2-O-CH2-)

Fig. 4.2 Formation of quinone intermediate

 §h“_P"I4_ e _ _ _ __________ db u__

b. Reaction between quinone intermediate and rubber

The quinone intermediate combines with a rubber double bond in a 1,4­

cycloaddition (Diels-Alder type) reaction to give a product with a chroman
structure. Subsequent dehydration and a second addition of a molecule of rubber

OH CH3 OH G
give the crosslinked product.

RRR'
O

CHZO R' CH’ cu on R. RI|___ C Rm 2

CH3

R"——-— C _":-_ CH ———R"'

R"' R»
O1 CH3 cu Ir
RI!

R=C15H31 _,,

R‘ :_—-_ Cl-j2__
R“ --= CHz——
0/ R IR
\"N

Fig. 4.3 Reaction of phenolic resin with elastomers (Chroman mechanism)

 o _ h em __ Ageing Studies on Rubbers Mfldtfiéd By §I;-P7_1_B1f0*l*WHf’xf §€§i?{

/I
(2) The ally! hydrogen mechanism

at Formation of quinone methide

OH
O

R ,/’ R
————-3­

<:H10H\ l R /CHZOH H20 cHzOH\{l:k/ CH,

Fig.4.4 Formation of quinone imtermediatc

b. Reaction ofquinone intermediate and rubber

O-methylene quinone abstracts an ally] hydrogen from the unsaturated mbber.

Chapter 4

R" -CH2 ~ C=CH ~ R' R'

CHpH

'Cc I
~

-0
CH, ' "

CH
CH
I
C~C
11
1

CH,
I
R"

R" -CH2 -
I
C=CH - R'
j
R'

L OH
I'
lX
.>: CH CH, - ,
I ~ CH

CH,-C 1 -0 I

I1 R C-C~
CH I1
I CH
R" I
R"

R=C , 5H 3, -n

R' = CH2-

R" = CH2-

Hg.4.5 Reaction of phenolic resin with elastomers (Allyl hydrogen

mechanism)

138
_ _ _ _ g_ ;Agein_g Stuflies on Rubbers Mfgdrfijed By? §‘§i§L;PllPt§Q1-lH¢ffl*l?€Sftl

c. Reaction between NBR and phenolic resin (36)

CH OH
OH l
| NH OH
In the case of NBR, CE N undergoes a different reaction with PF resin.

2 CH2OH | HC —c — 0 -— CH2 cH2o|-1

+ C}-|— CiN --—-——i|- l

Fig. 4.6 Reaction between NBR and phenolic resin

Sulphur crosslinking ofthe monomeric units also usually happens along with
resin crosslinking.

Ln this study, the effect of incorporation of the resin into various elastomers
has been investigated in terms of the retention of mechanical and other physical
properties.

4.9 RESULTS AND DISCUSSION

The resin prepared by the condensation of CNSL- phenol- formaldehyde

(Section 2.3) was added to various elastomers to observe the effect on elastomer
ageing properties. Different proportions of the resin were milled into each rubber
compound during the mixing process. The properties ofthe resin cured rubber afier
various periods of ageing at 100°C were evaluated and compared to investigate the
role ofthe resin in improving the ageing properties.

ln the case of SBR and NBR a more exhaustive study was conducted in
order to understand the effect of stoichiometiy of the resin on the properties of the
vulcanizates.

4.9.1 NBR- Effect of resin on the ageing properties of vulcanizate

a. Resin content

I. Effect of resin content on the properties of vulcanizates

In this study resin with P: F ratio l: 2.9 and CNSL: P 1: l is used.

77 7.7
Chapter

t‘
1 Ii
1‘
4 7 7 7 7 7 7 7 7 7 7 7 7 77 7 _ 7 _i* 4 7

7l U_t
1. Tensile strength

01 ‘t1; it

ll

\
t
: iv =* 1%
can-oou—-—~----4»—-~--aw-¢-—-»--aqua--o-----Q-Q-_~=. —_——_—¢:—--¢._——_;:: f~—_-7 _—7__ -. 7 7 74 _ _7 i j 7____;:______7_~--;,,.‘i

i,

O 5 10 15 20 25 30
i77 77 77 ______77_ 777 __ 7 _7__ 7 7_ 7 7__ 7 7 77 77 7 __ 7__ 7__ ____ __ 1'

Resin content (phr)

ii

Fig. 4.7 Variation of tensile strength with resin content of N BR

Fig. 4.7 shows the variation of tensile strength with resin content on NBR.
Addition of resin decreases the tensile strength ofNBR vulcanizates. This tendency
increases as the resin content goes up. The reduction in tensile strength as the resin
content increases can be attributed to the plasticization effect of the resin (37) or
the slow rate of crosslinking reaction involving the rubber and resin (38).

4
2. Elongation at break

Q00 t.....-..,..7-..s.--.....77....77...,.77..7...-7-....._..t......_...,...-...7.-_7777......-7........t.._n....7..t

800
600 A;
/— -1 i cl F"** 2*
400 l
200
O 5 10 15 20 25 30 Resin content (phr)

Fig. 4.8 Variation of elongation at break with resin content of NBR

Fig. 4.8 shows the effect of addition of resin on the elongation at break of
vulcanizates. Elongation at break shows a marginal increase HS resin content iI1CI‘6ases
 t Ageing Studies on Rubbers Modified By Cg'Ng5L-P7181101-[1818 Resin

3. Modulus

4 __ _” , _ ____H_‘_ ,_,_______,_,;,,___, - :,,_;_-_~,;_, _—..'.'.;.;__=_' _ _____"I-‘_“_‘.2‘.;.T. _-.1--.......~.-....._.............-.._......-..-,.......~........._._\

I?

45

ll

3* 1% _
l

it
l:

it

1 -t

lt

Q
0 5 10 15 20 25 30
l
ii

Resin content (phr)

Fig. 4.9 Variation of modulus with resin content of NBR

F ig. 4.9 shows the variation of modulus with resin content. As resin content
increases modulus decreases. Possibly the long side chain of CNSL gives
flexibility to the vulcanizates and reduces the modulus.

4. Tear strength

.,.--»-“ _...».-,.“..- ,“..-»“-.-...».~....-,...,..-...\........,-\.,>~‘~_\...~.-_...~.~....,....-..-.-..--.- ...-.,-...--~~”~, .- - Ma“. --... ..»..-..- --~w-~- -------- ‘~\

)
5

!
?
1

tr

F
i

0 5 10 15 20 25 30
— _—_ --~ _ ; — — >.'-1,, ~ ;— ,, I _' , ~ ~ _, ~ ~-_,_ — _,;' AW... W;_,,--~W;,__...3

Resin content (phr)

Fig. 4.10 Variation of tear strength with resin content of NBR

Fig. 4.10 Shows the effect of addition of resin on tear strength of NBR
vulCa11iZ8t@$- Tear Strenglh decreases as resin content increases from 15 phr
onwards. The resin can lead to reduction in ciystallinity which is one of the factors
Chapter4 __ _ _ _
5. Compression set

80 ‘qi—_—_-can
t

t
_::::_ —::':_=o.~'
411:7: '~'-':o-u.i—_—:~:a-----o-—----.~-u-u->-ee--n-o-----—va~»>ne-:-----u-~¢-o-.-- t 727;. +_'=\-.v_i__.._.'-">_.__".-_-_;¢.-:1;­ it

5.
1. lé

t.
l

if
‘l

1!
1

40 ii

O 5 10 15 20 25 30
\_ ____. ____i__. _ _._ ____.__. _. _. ___.. _____ . _ __ __.. ___ _ _ .ll

Resin content (phr)

Fig. 4. ll Variation of compression set with resin content of NBR

Compression set increases linearly with resin content (Fig 4.11).

Compression set indicates loss of elasticity and resilience of the rubber. The
presence ofthe resin is responsible for this.

6. Swelling index

2 ‘-.~..-.__...~.-~.-..,....----_~.-..-.~.-~.-..~.. ........-.~\.~........-....~.~.-\ -1-.»_ ».~~ -_.'_.~..A;'_~ -.._.__' —=.-.'.~=_»__g_~..~_'_ _;. _;:.-.-_'_.....~...-.e_<.-.-,_­ ” "Tl
l 1!

‘>

l.
l

1.5 ­ l

0.5
0O 5 10 15 20- 25~30
l

I
1:

it
i

-r
J

Resin content (phr)

Fig. 4.12 Variation of swelling index with resin content of NBR

The effect of resin content on swelling index is shown in Fig 4.12. The
swelling index is seen to increase only slightly with increase in resin content.
 Ageil1g Studies 011 Rubbers Modified By CNSL-Phel1ol- Hexa Resin

7. Abrasion loss

25

o \
o 5 10 15 20 25 30 '~
Resin content (phr)

Fig. 4. 13 Variation of abrasion loss with resin content of NBR

Variation of abrasion loss with resin content is shown in Fig 4.13. Abrasion
loss values increase with increase in resin content which can be due to higher
percentages of uncrosslinked material at higher resin percentages.

8. Acetone soluble matter

16
~
~
14
'.; 12
E 10
~
.c 8
~
'0 6
~
~
0 4
0

..
0;
c
2
0
0 5 10 15 20 25 30
Resin content (phr)

Fig. 4.14 Variation of with acetone soluble matter with resin content of NBR

Acetone soluble matter increases as resin content increases. Acetone soluble

matter is the uncrosslinked resin present in the rubber. At higher percentages of
resin the acetone extractable matter is naturally more (Fig. 4.14).

143
Chapter 4

9. Density

U 1.5 ~---+---<.----+-------.
o
E
.:!!
~
.~

c
~
Cl 0.5

OL- ----l

o 5 10 15 20 25 30
Resin content (phr)

Fig. 4.15 Variation of density with resin content ofNBR

As the resin content increases, the average density goes up marginally as can
be expected.

II. Effect ofresin content on ageing properties ofNBR vulcanizates using

Formulation I.

In this study resin with P: F ratio I: 2.9 and CNSL: P 1: 1 is used.

1. Tensile strength

10 , . . . . . . . - - - - - - - - - - - - - - - - - - .

t~ :[=::=:~~~~
7
-+-RO
......... R5
~~ L_----------..
6
5
........... R 10
~R15
-:;; 4
.!! ........... R 20
·in 3
......... R25
....~ 2
1
0'-------- _
o 25 50 75 100
Ageing time (hours)

Fig. 4.16 Variation of tensile strength with resin

content for NBR vulcanizates.

144
_r g Ageing g5tudie_s on Rubbers Medified By CNSL-Fheiiolg Hera Resin’

Fig. 4.16-4.18 show the effect of ageing for different periods (24 hours, 48
hours, 72 hours and 96 hours) on mechanical properties of the vulcanizate
containing different percentages of the resin as ageing stabilizer using Formulation
l. Referring to Fig 4.16 tensile strength of samples containing lower percentages of
the resin (O~l0 phr) decreases steadily as the ageing period increases. But for
higher resin samples (15-25 phr) tensile strength after ageing shows an increasing
tendency. After 96 hours ageing the tensile strength for the high resin samples are
marginally higher. Beyond 96 hours, the high resin samples may gain strength
further. It is likely that rubber— resin interactions will continue to take place as the
ageing process continues. This may be attributable to the post curing reactions
taking place in the vulcanizate during the ageing period, resulting in additional
crosslinks and leading to an increase in cross link density (39, 40).

2. Elongation at break

-_ 800
0F§iti-1-
-0- A
R 0
900 .... .......s......... ......

A +R 5
i.Il'
V -0-R25
oi 1‘ i
R 10
0 20 40 60 80 100 120
Ageing time (hours)
—><-R15
—xe--R20

Fig. 4.17 Variation of elongation at break with resin

content for NBR vulcanizates.

The elongation at break (Fig. 4.17) is comparatively high for the high resin
samples. But as the ageing period increases the fall in elongation at break is steeper
for the high resin samples. Rubber-resin interactions causes a gradual fall in
elongation as ageing proceeds.
 ;1‘ illit
€'1~2'¢'.4___ _- . . _ . s _ _ _ __.s-_ _

3. Tear strength

7 f._..-....-a..._._ -_s__.___ _W__..-s__,__, . __..-_s.;__.._.__..n$..;;;..;.;:­

i; :— _ I -0-R0
~: 1 r -ii-R10
1 =_.“' R
0 L;_.._., . 7 W ,_..__. ‘,_,_.,,:_W:.__ . _ so _ _..__n __ _ _ .__ ___;­
0 20 40 60 80 100 120
Ageing time (hours)

Fig. 4.18 Variation of tear strength with resin content for NBR vulcanizates

Fig. 4.18 shows the effect of ageing on tear strength of samples containing
various percentages of resin. Here again, at higher percentages of the resin the tear
strength steadily increases with ageing period. After about 50 hours ageing there is
a fall in tear strength in the case of low resin samples.

lt is clear that the crosslinking process proceeds at an extremely slow rate.

The positive effect of incorporation of the resin is noticeable only beyond 20 phr
resin. Ageing studies leading to prolonged periods are necessary to establish long
term ageing properties. The age stabilization can be attributed to slow crosslinking
reactions involving the resin and the rubber which take more than 96 hours for
completion.

b. P: F ratio of resin

In this study resin with CNSL: P ratio 1:1 and resin content of 25 phr and
P:F ratios l:2.9, l: 2.3, l:l.7 and l:l.l were used.
 Ageing Studies on Rubbers Modified By CNSL-Pllenol- Hexa Resin

The moulding studies using the first formulation was modified by reducing
the filler content because the compound become very sticky during mixing. So for
the following cases Formulation 11 was used.

1. Tensile strength

15
<ii 14
a.
~ 13
s: _ _ RO
C, 12
c: ___ P:F 1:2.9
E
u; 11 ---.- P:F 1:2.3 I

~ ---*-P:F 1:1.7
.iij 10
e -Jl-P:F 1:1.1
...." 9
a
0 2 4 6 a 10 12
Ageing time (Days)

Fig. 4.19 Variation of tensile strength with ageing time of

NBR vuleanizates eontaining resin with different P: F ratios

Fig. 4.19 shows the variation of tensile strength with ageing time of samples
containing P: F ratios, I: 2.9, 1:2.3, 1:1.7 and I: 1.1.

The immediate effect of adding the resin was to lower the tensile strength of
the unaged material. This can be attributed either to the slow curing nature of the
resin or to the slow rate of cross-linking reaction involving the resin and rubber.
The tensile strength of the vulcanizate without added resin decreased with ageing
time. The reduction in tensile strength may have been caused by a decrease in the
number of polysulfidic crosslinks and an increase in the number of monosulfidic
ones, or by network disruption resulting from backbone chain scission and
crosslink rupture (12- 15). Each backbone scission creates two chain cnd segments
attached to the network at one end. These segments have non-load-bearing effects
and can be expected to lower the strength.

The tensile strength of vuleanizates containing resin increased with ageing

time. This points to the formation of additional network chains resulting from
crosslmking between the resin and the NBR (39,40). The increase in tensile

147
 A
Chapter 4
_**__*_***____** _ _ _ __****_?_ _— _?i_*_i_i 4 7~—

strength during ageing is most obvious for vulcanizates with P: F ratio 1:l.l. The
improvement of properties on ageing was more pronounced when a resin
containing a relatively low amount of fonnaldehyde was used. The shape of the
tensile strength curves when resin is added is typical of resin cured systems. From
the standpoint of the stability of properties on ageing, a resin with P: F ratio l: 2.9

700
can be considered the best, as the change in tensile strength was least. Such a resin
completes its reaction with rubber at an early stage of ageing, hence the high initial
tensile strength values.

2. Elongation at break

li - ­
‘ll

it

if -—-I-— P:F 1:2.9

"' I, —-X-——P:F 1:1.7

100 ­
,, --i-PZF 122.3 _

-—'X-"PCF lI‘l.1
ll

O 2 4 6 8 10 12
ll

Ageing time(Days)

Fig. 4.20 Variation of elongation at break with ageing time of NBR

vulcanizates containing resin with different P: F ratios

Fig. 4.20 shows the variation in elongation at break with ageing time of
samples containing P: F ratios l: 2.9, l: 2.3, l: l.7 and 1: 1.1- There was a general
increase in elongation at break on addition of the resin. The effect was greater for
resins containing less formaldehyde. This can again be attributed to the smaller size
ofthe molecules when more formaldehyde was present. However, in all cases there
was a steady reduction in elongation at break on ageing suggesting a more
crosslinked structure­
3. Modulus

l‘
1
75

-I-—P:F 1:2.9
__ 3 -fil-PfiT2§3
‘i:=“"“"'i § -—¥&-F%F1;t1
O 2 4 6 8 10 12
Ageing Studies on Rubbers Modified By CNSL-Plienok ficxa Resin

o ag~ge~ new new W M ~ue e ~;~~w M es» w~e~i

l § -ae-Pi=1:i7

Fig. 4.21 Variation of Modulus with ageing time of NBR

vulcanizates containing resin with different P: F ratios
The tensile modulus was also lower for unaged samples containing resin
Ageing time(Days)
-0-—R O

1.
than for those without resin. As the ageing time increased the modulus increased
for all the samples (Fig. 4.21). This could have been due to the stiffening of the
vulcanizate as ageing proceeds. The resin with a P: F ratio of l: 2.9 showed the
greatest effect. Interestingly, samples without resin also showed increasing

1‘ 1.
modulus on ageing. Stiffening due to degradation can be the reason for this.

4. Tear strength
twp...-.-t..._--_ ...-..-..-.-........-._.......... ...... .. ----»-~..\....,......M.-._._.....,..-........,....,....,.,_..,... 0...-...».......,..-.-.-.-._--.-..,_.......~_.........\,..... \- ._»--\--~..........

~' 40 g ---Pr=1:19
a+<a§n:4:Ir-@4~;'|IliEf—i1—‘i —»-R 0

i *§ —)(—P:F 1;1.7
l

' ——h—P:F 1:2.3

“ —€E—-Pf=1fl.t
00 2at4 it6 e8 10
_r__
12 Ageing Time (Days)

Fig. 4.22 Variation of tear strength with ageing time of NBR vulcanizates
containing resin with different P: F ratios
_¢!wP!¢1;4__,,.st __ -_ ta

12
Fig. 4.22 shows the variation in tear strength. The tear strength of the
samples without any resin decreased with ageing time and that of samples
containing resin showed very little change. Resins containing more formaldehyde
showed marginally higher tear strength. The resin with a P: F ratio l:2.9 gave the
best protection against a reduction in tear strength.

5. Loss in weight on extraction with toluene

8—~—R0
t + P:F 112.9
__ ' up -+- P;F1:2.3
_ T}
6

-- 4 ‘F " ———><-—P:F1:1.7
__ — 2 ti -—a|t—-P:F1:1.1y_
O 2 4 6 8 10 12
Ageing time (Days)

Fig. 4.23 Variation of loss in weight on extraction with toluene of NBR

vulcanizates containing resin with different P: F ratios

Fig. 4.23 shows the variation ofloss in weight on extraction with toluene for
vulcanizates with different P: F ratios. The extent of matter soluble in toluene
decreased with ageing time for vulcanizates containing resin due to the formation
of additional crosslinlcs in the vulcanizates. In general, extractable matter, rubber or
resin, is more in samples containing resin. There is very little change in extractable
matter with formaldehyde content.
 ~;
g _ _ Ageing Studies on Rubbers M0difie_d_By (INS_L-Plienolf Ijesra l{esm_

1.4 it if
6. Swelling index

1 _6 ,_.,,,,_;, as..._...ais..,.==...._.s._i..“-s....m......_...._,.~......_...,E

0.4
0.2 1
1

11

1
l;
I

ix
H

I
—0—RO
-—I——P:F 112.9
--A-—P;f1:2.3
—><-P:F 1:1.7
-39-P:F1:1.1

O 2 4 6 8 10 12 Ageing time (Days)

Fig. 4.24 Variation of swelling index of NBR vulcanizates

containing resin with different P: F ratios

Fig. 4.24 shows the variation of swelling index. Swelling index decreases as
ageing time increases. As formaldehyde content changes, there is veiy little chanui
in swelling index
Chapter?“ as any _ s
7. Loss in weight on extraction with acetone
{-0
“.­

.­
1‘\ 10
8 ; ‘FM -—0-R0
1 . t,...._.....-.-._.......,-.....-.-....~__~; '._‘—‘T*—‘r'_-_*_‘;;_*_'-_:;- _a _ €_*_. at __......»a__~___g-fa

——I-—P:F1:2.9
6 -—a—P:F 112.3
Qi

J aw 1
4% —-X-—P:F1:1.7 —->K— PIF 121.1

0 2 4 6 8 10 12
Ageing time (Days)

Fig. 4.25 Variation of loss in weight on extraction with acetone of NBR

V
vulcanizates containing resin with different P: F ratios
Fig. 4.25 shows the variation of loss in weight on extraction with acetone
Acetone soluble matter is more in vulcanizates containing resin. There is not much
change in weight on extraction with acetone with formaldehyde content.
c. CNSL: P ratio

I. Tensile strength
In this study resin with P: F ratio l: 2.9 and resin content 25 phr was used.

18 .-.-_—==:.-.;-,-_;;~_-_-_-.'_-.=. .'*;_=-=-_.*=:_‘:;_.':_ .-~; . - ";‘-'-'—“%*-:l'-'~'-"‘;~?v"';‘- ».= ~=_ —~ — .»_<,- = .T

il

1‘

§\ 16 ‘I

ii

aear-ri 1_ g*+*
_ T ii "“ =1
—-O-—CNSL:P100:0
L *”* 4 V: Fe +;¢;ea¢; 4»-= ——I-—CNSL:P 75:25
' ——l-— CNSLIP 50:50
_ —-X-— CNSL:P 25:75
*‘ ——X-—- CNSLIP 0:100
4!

D2468 Ageing time (Days)

10 12

Fig. 4.26 Variation of tensile strength with ageing time of NBR Vulcanizateg
containing resin with different CNSL: P ratios
 g Ageing Studies on Rubbers Modified By Cl\l$L-l’hert0l- l_1ext1_Resr'ri

Fig. 4.26 shows the variation in tensile strength. The tensile strength of the
samples showed only a marginal increase with ageing time. As the CNSL content
increased the tensile strength of the vulcanizates decreased. CNSL is less reactive
than phenol. Crude CNSL also contains constituents that may not react with
formaldehyde. The structure of CNSL is less conducive to a compact crosslinked
structure in comparison with phenol. For these reasons, increasing amounts of
CNSL leads to lowering oftensile strength.

800 "
2. Elongation at break

909 . __- -.. - .... .. ...-.-.-..........-..........-.-.......€

p-Q ‘ ,
y,
%-I l
-0- CNSL:P 100:0
500 t‘ _ --I-—-CNSL:P 7525

100 J
— T: -—)(-— CNSLIP 25375
fi _ -—i—CNSL:P 50:50
00 2 4 6at8 10
~ 12
at
Ageing time (Days)
Q —ax—- CNSL:P 0;1oo

Fig. 4.27 Variation of elongation at break with ageing time of NBR

vulcanizatcs containing resin with different CNSL: P ratios

Fig. 4.27 shows the variation in elongation at break. As the CNSL content
increased, the elongation at break increased. The long aliphatic chain of the CNSL
molecule leads to higher plasticity. llence samples containing more CNSL show
greater elongation. Ageing has the effect oi‘ reducing the elongation oliall samples.
Chapter 4

3. Modulus

-+-CNSL:P 100:0
_ _ CNSL:P 75:25
.-a- CNSL:P 50:50
-->E- CNSL:P 25:75
-lE- CNSL:P 0:100

o L- ----- --!

o 2 4 6 8 10 12
Ageing time(Days)

Fig. 4.28 Variation of tensile modulus with ageing time of NBR vnlcanizates
containing resin with different CNSL: P ratios

Fig. 4.28 shows the variation in tensile modulus. As the CNSL content
increased, the modulus decreased. This may he due to the long side chain ofCNSL,
which can create steric hindrance to the crosslinking reaction. Ageing improves the
modulus in all cases although to a lesser extent when more CNSL is present.

4. Tear strength

70 -_._--
_ 60
-~
E
..§ 50 .
1E. ;; ,,~ -+-CNSL:P 100:0
£ 40 - - CNSL:P 75:25
C>
0 -a- CNSL:P 50:50
e
-;;;
30
-->E- CNSL:P 25:75
~ 20 -lE- CNSL:P 0:100
~
~
f-
10

0
0 5 10 15
Aging time (Days)

Fig. 4.29 Variation of tear strength with ageing time of NBR vulcanizates
containing resin with different CNSL: P ratios

154
 !
f _ gAgeiug Studies goirglghgzlabers Mogdifiedfiy SgIs-flP!ie1g:g0g1- T-IexagResgz'n_

Fig. 4.29 shows the variation in tear strength with ageing time of vulcanizates
with different CNSL: P ratios. There is a general but slight increase in tear strength
on ageing. As CNSL content increased, the tear strength decreased. This could have
been due to the lower reactivity of CNSL due to the presence of side chain.

5. Loss in weight on extraction with toluene

14 .......... M..- ......................................... ......... .,___c,.c_....,....i..__~.......-.

—

"" 10 -0-—
"“ —-I—— R0100:0
CNSLLP
;i --A—- CNSL:P 75:25 —~>(-— CNSL:P 50:50
-- ii‘ —-i|t—CNSL:P 25:75
-4- CNSL:P 0:100

0 2 4 6 8 10 12
Ageing time (Days)

Fig. 4.30 Variation of loss in weight on extraction with toluene with ageing
time of NBR vulcanizates containing resin with different CNSL: P ratios

Fig. 4.30 shows the variation of loss in weight on extraction with toluene of
NBR vulcanizates with different CNSL-: P ratios. As CNSL content increases the
extent of matter soluble in toluene increases. The compactness of the vulcanizate
decreases due to the long side chain of CNSL. Matter soluble in toluene decreased
with increases ageing time due to progressive crosslinking between resin and
mbber
6. Swelling index

-1|

-1
-1
~—­
18
§1a@2*e-ks,,,_ei,,,_,_,,__ _ sees

1.6 =­
1.4
1.2

0.8
0.6
0.4
.1
i qt,‘

‘*0-0—0—-0-0-0-Q-0-Q-0
1
-“-“‘5-A
1.
1.

j.

,,

1.
i.

|.

|.
-O-— R0
——I—— CNSL:P 100:0
-—i—- CNSL:P 75:25
-—-X-— CNSL:P 50:50
-9!-— CNSL:P 25:75
2‘

0.2 -0- CNSL:P 0:100

O 2 4 6 8 10 12
Ageing time (Days)

Fig. 4.31 Variation of swelling index with ageing time of NBR vulcanizates
containing resin with different CNSL: P ratios

Fig. 4.31 shows the variation of swelling index. As CNSI. content increases
swelling index increases.

7. Loss in weight on extraction with acetone

12

.-.
+4
10
/-\ --0-R0
Q.‘ 8
\i'
—I— CNSL:P 100:0
6
J—'
t

——A-— CNSL: P 75:25

-1-. 4
“‘*"xc.s ——)(-— CNSL:p 50:50
-——§-— CNSL:P 25:75
-—O-— CNSL:P 0:100
0 1

O 2 4 6 8 10 12
Ageing time (Days)

Fig. 4.32 Variation of loss in weight on extraction with acetone with ageing
time of NBR vulcanizates containing resin with different CNSL: P ratios
 Ageing Studies 011 Rubbers Modified By CNSL-Pltello1- Hexa Resin

Fig. 4.32 shows the variation of loss in weight on extraction with acetone.
Loss in weight on extraction with acetone decreases as ageing time increases. More
and more of the resin get incorporated in the vu1canizate as ageing time increases.
As CNSL content increases, matter soluble in acetone increases. This is due to the
unreaeted CNSL present in the vu1canizate at high CNSL contents.

4.9.2 SBR- Effect of resin on the ageing properties of'vujcanizates,

a. CNSL Content.

I. Tensile strength

__ co
___ C5
___ C 10
o I~-
o 2 4 6 8 10 12 ~C15
-ee-. C20
Ageing Time (Days) _ _ C25

Fig. 4.33 Variation of tensile strength with ageing time of SBR vulcanizates
with different CNSL contents (C 0- Ophr CNSL, C 5- 5 phr CNSL, C 10- 10
phr CNSL, C 15 - 15 phr CNSL, C 20- 20 phr CNSL, C 25- 25 phr CNSL)

Fig. 4.33 shows the variation in tensile strength with progressive ageing. The
immediate effect of adding CNSL is to decrease the tensile strength of the unaged
material marginally. This can be attributed to the slow reaction between CNSL and
rubber. Tensile strength of vu1canizates without any CNSL and those containing
lower than 15% CNSL decreased noticeably with ageing time. The presence of
CNSL is seen to retard the ageing action at higher percentages of CNSL (like
25%). The antioxidant behavior of CNSL by virtue of the substituted phenol
structure may account for this.

157
 it
7Chapter
7 7 7 74 ,7 7 ._7 .7 7 7 7 7 7 7 _ 7 7 _ _ _ _~i_i_ __ 7 i i__i r*_ 7 7,7 ___ 7 _

800
\135:
2. Elongation at break

l—'.'-‘C25
+¢0
1000 _.;;_».._;....._..--a g . W .._---_-i.-#:.»..:.s7.

.Z ,1
600 it I
A it -0-cs
f —A——C10
ir

vi

\ it
4001f
200 M
'
0 r r ——3l——C20T­
r -\ it —><—-015

0 2 4 6 8 10 12 Ageing time (Days)

Fig. 4.34 Variation of elongation at break with ageing time of SBR

vulcanizates with different CNSL contents

Fig. 4.34 shows the variation in elongation at break with CNS], content.
There was a general increase in elongation at break on addition of CNSL for the
unaged material. At initial stages of ageing elongation at break falls for all the
samples. Elongation at break decreases soon after due to additional crosslinking
and stiffening of rubber chains. But it stabilized after about 2 days of ageing. All
the ingredients of CNSL have high boiling points. The plasticiser action of CNSL
is hence sustained even after prolonged ageing
 g g_ _ g_ _ Ageing Studies on Rubbers Modified By CN*5If--APl18{IQl- flfxf §8$fri

3. Modulus

"‘ -+-co
-' +010
2 —-I-C5
_l
4 5 __-.._..s___.:._:......._.,....:.*._...... ...... -....-..._................. ...... ._...... ............... -.-\
4

- ll t -x-C15 -—X-—-C20
F --.-C25
i

0 2 4 6 8 10 12 Aging time (Days)

Fig. 4.35 Variation of tensile modulus with ageing time of

SBR vulcanizates with different CNSL contents

Fig. 4.35 shows the variation in modulus. Modulus of all the samples
increased with ageing time. This could have been due to the stiffening of the
vulcanizate as ageing time increased- Some interaction between CNSL and rubber
is indicated.

4. Tear strength

89 .-...~.._......-.~.. ..M-.._-..._W__...... ....,. _.e...M,..,....._._.-., .....-... .. ..

--50 2 '
§;‘-i-—a-cio
*1
C5
_;
j -O—-C0

. -—O—C25 —: —- A *—I=I;—l —au-020

QO 2 4-_
6 8 10 _
12 Ageing Time (Days)
2

Fig. 4.36 Variation of tear strength with ageing time of

SBR vuleanizates with different CNSL contents
Chapter 4

Fig. 4.36 shows the variation in tear strength. The immediate effect of
adding CNSL is to lower the tear strength of unaged vulcanizates. Tear strength of
the vulcanizates without any added CNSL and those containing lower amounts of
CNSL (0-15 phr) decreased with ageing time in the beginning. Tear strength
values largely remained steady on further ageing for all the samples. The presence
of CNSL is seen to retard crack generation and propagation. This is likely to be
related to the long chain substitution which can lead to chain entanglement.

b. Resin content
1. Tensile strength

16

~£ 14r~a:Ei~~
~ 12
10
-+--RO
____ R 5

C> ......... R10

~ 8 ~R15
;; 6 --ll-- R 20
~

~ 4 _ _ R25
c
~ 2
o l --'

o 2 4 6 8 10 12
Ageing time (Days)

Fig. 4.37 shows the variation of tensile strength with ageing time of SBR
vnlcanizates with different resin contents (R 0- Ophr resin, R 5- 5 phr resin, R
10- 10 phr resin, R 15 -15 phr resin, R 20- 20 phr resin, R 25- 25 phr resin)

Fig. 4.37 shows the variation in tensile strength with ageing time of
vulcanizates containing different percentages of phenol- CNSL- hexa resin. The
immediate effect of adding the resin is to increase the tensile strength of the unaged
vulcanizates. This can be due to additional crosslinking reactions involving rubber
and resin. Tensile strength of vulcanizates without any added resin and those
containing lower percentages of resin decreases with ageing time. Tensile strength
of vulcanizates with higher amounts of resin content on the other hand increased
with ageing time. This indicates additional network chains resulting from
cross linking between resin and rubber. Samples containing resin maintain higher
values of tensile strength at all stages of ageing.

160
 g _ _ Ageing Studies on Rubbers Modified? ASL?-_PIg1f'n_ol-_Hexa_Re-siii

1200
2. Elongation at break

000 t --0- R 0
i 3 5 -—a-R10
it —-)(—- R 15
" 40° ; -" "=45;-x _ _ —*-R 20
_ 200 t 1? ___t ‘ -0- R 25
0 2 4 6 8 10 12
0 >e»W~e;:e~~-.~:~~e=~-»e»~~- e~~~ e»-3 »e>

Ageing time (Days)

Fig. 4.38 shows the variation of elongation at break with ageing time of SBR
vulcanizates with different resin contents

\1%
4:;2
Fig. 4.38 shows the variation in elongation at break with resin content­
Addition of resin increased the elongation at break of unaged vulcanizates

‘ ;
indicating some plasticizing action. But it decreased with ageing time at initial

._ 2
stages of ageing. After about 2 days the values get more or less stabilized.
Crosslinking oi‘ the resin and progressive reaction with the rubber may be
responsible for this.
3. Modulus

0.5
3.5 5; —-0-R0
4 5 -W..__.W-.-a-.__w..._....-__....-_.te-_..~.......-......,.........-..-..-.........
i

3 i ; —1I—F25
-— —x—-R15
e gr ~—l|—R10
1 -0-R25
00 2- 4 6 8so10 12
_.
; -"X"-R20

Ageing Time (Days)

Fig. 4.39 Variation of modulus with ageing time of SBR vulcanizates with
different resin contents
Chapter g g

’
i
.i‘ij
.
t at
X
it
W
ia
* —‘
ta _-t -—)(—-R15
. —o—R25
I

O 2 4 6 8 10 12
__

Fig. 4.39 shows the variation in modulus with ageing time of vulcanizateg

‘I
containing different amounts of resin. Modulus of all the samples increased with
ageing time. This may be the result of stiffening of chains as ageing proceeds.

70
4. Tear strength

‘E 1
so _- ....... »

10
i .. ~Q_ 0 so
‘p.""r - .
Ageing time (Days)
—O—R0
1 —I—-R5

Fig. 4.40 Variation of tear strength with ageing time of SBR

vulcanizates with different resin content

Fig. 4.40 shows the variation in tear strength with ageing time of
vulcanizates containing different amounts of resin. Vulcanizates without any added
resin showed a sharp decreasing tendency with ageing time in the beginning. Tear
strength of vulcanizates containing higher amounts of resin increased with ageing
time. This again points to the progressive reactions in the blend as ageing proceeds.
 Ageing Studies 011 Rubbers Modified By CNSL-Phenol- Hexa Resin

5. Swelling index

3
x
'"
D
.~
2.5
2
- _ _ Ra
0>
~
1.5 -. _ _ R5
~

'" 0.5
~
Ul
1
---.- R10
~R15
0 R20
-ll!-
0 2 4 6 8 10 12 _ _ R25 ,
',1;'
Ageing time (Days)

Fig. 4.41 Variation of swelling index with ageing time of SBR vulcanizates
with different resin content

Fig. 4.41 shows the variation of swelling index. Swelling index decreases as
ageing time increases. This indicates increasing levels of cross linking on ageing
which is along expected lines.

6. Acetone soluble matter

10 _._ ~ _~-_ - ...•.,

g
_ _ Ra

!~~
_ _ R5

---.- R10

~t-~=:~:::::::::=:~t:::;~~ ~R15

R20
-ll!-
2 _ _ R25
1
o
o 2 4 6 8 10 12
Ageing time (Days)

Fig. 4.42 Variation of loss in weight on extraction with acetone with ageing time of
SBR vulcanizates with different resin content

Fig. 4.42 shows the variation in loss of weight on extraction with acetone.
As ageing time increases the matter soluble in acetone decreases. It indicates that

163
€herit¢ré_oriirr,rr_ _ri _ r
more and more resin gets crosslinked or alternatively, gets incorporated into the
network as ageing proceeds. The sample not containing the resin also shows the
presence of low molecular weight extractable matter. At low resin percentage, say
5%, the extractable matter afier 10 days of ageing is not very different from that of
the sample containing no resin. So at this resin content it can be assumed that the
resin has fully and inextricably integrated into the rubber.

16 1
c. P: F ratio of resin

hi this study a resin with CNSL: P ratio 1:1 and resin content 25 phr was used­

l. Tensile strength

2l11ll
I ___.t:g%: I-*""'-:fit:.'i*

4fl 1
ti
14

i F it —0—R0
8<;——t——P:F
—-I—-P:F 112.3
1:29
ii

6 ii

U1
--x-P;F
jg
at
1;1.7
-902-—-P:F1:1.1
O 2 4 6 8 10 12
l

0 L;-o,_g f 2 ,2 1. .._e._- 1 _.o,,_ _ , _ _ A"_T7'_ FT’ _ _-._ _1

Ageing time (Days)

Fig. 4.43 Variation of tensile strength with ageing time of SBR

vulcanizates with resin having different P: F ratios (P: F refers
phenolzformaldehyde ratio)

Fig. 4.43 shows the variation in tensile strength with ageing time of samples
with P: F ratios l: 2.9, 112.3, 111.7 and l:1.l. The tensile strength is higher when a
resin containing higher amount of formaldehyde is used. Vulcanizates having resin
with P: F ratio 1: 2.9 showed almost constant tensile strength. Such a resin
completes its reaction with rubber at an early stage of ageing and shows high initial
 _ _ __ _ Ageing Studies on Rubbers Modified By_QN51:-1371131111-_HfXQRlfif

?-0-3; '—.-
ii l ii
tensile strength values. Without the resin, there is rapid fall of tensile strength on
ageing.

600
1000
2. Elongation at break

1200 .... _...___.a....... ..... -._........,--.._.a..=_..........s.;_...__ ._ _ :_.,..= ........ -..... ....... -...... ..................... -3

O
P:F 1:2.9
fl

A. —i—-P:F131.7
1;2.3
ll

_400
—-$(—-—P:F
it -—)\t-—P:f1:1.1
00 2 4 6 8 10412
200 Z‘

Ageing time (Days)

Fig. 4.44 Variation of elongation at break with ageing time of SBR

vulcanizates with resin having different P: F ratios

Fig. 4.44 shows the variation in elongation at break with ageing time of
samples with P: F ratios l: 2.9, l:2.3, l:l.7 and l:1.l. In all cases there is a
reduction in elongation at break on ageing at the early stages. The presence of resin
leads to greater elongation and lower formaldehyde content is conducive to higher
levels of elongation at break.
Chapter 4

3. Modulus

-+-0

- ~
... _ _ P:F 1:2.9
.....-P:F 1:2.3
~P:F 1:1.7
~P:F 1:1.1

o
o 2 4 6 8 10 12
Ageing tme (Days)

Fig. 4.45 Variation of modulns with ageing time of SBR vulcanizates with
resin having different P: F ratios

Fig. 4.45 shows the variation in tensile modulus. As the ageing time
increased the modulus increased for all the samples. This could have been due to
the stiffening of the network as ageing proceeds. Vulcanizates containing resin
with P: F ratio I :2.9 showed the least variation in modulus on addition of resin. In
all cases, there is a rapid fall in modulus at early stages of ageing. The increase in
modulus is maximum for a P: F ratio of I: 1.1. At low formaldehyde content (P:
F= I: 1.1) the condensate will have more benzene rings per molecule. This may
affect the chain flexibility and lead to a higher modulus.

4. Tear strength

80
E 70
.E
z 60
s: 50
Cl
o
40~'''''-''
e 30 -+-0
~ 20 _ _ P:F 1:2.9
~ 10
... .....-P:F 1:2.3
0'---------------' ~P:F 1:1.7
o 2 4 6 8 10 12
~P:F 1:1.1
Ageing Time (Days)

Fig. 4.46 Variation of tear strength with ageing time of SBR vulcanizates with
resin having different P: F ratios

166
 is 1 g g_ __ Ageing Studies on Rubbers M_0dified_BgygCl\]€iL:I{her1ol1 Ifesrailiesili

Fig. 4.46 shows the variation in tear strength with ageing time of
vulcanizates with different P: F ratios. Tear strength of samples without any resin

3l
decreased with ageing time. P: F ratio has very little effect on the contribution of
the resin to the tear strength. In the presence of the resin, high values of tear
strength are sustained upon ageing.

5. Swelling index

3 Q­ 3 a.-----..-.~»»_~~---v<a-->-~-we-_-¢—--pa--av--snui-.p--Q-vq-_w~-w-u---~....-.9-.~.---Q».--....,-_\.-~. .-ea».-4-->~.---.<v-npq
i

“E I7 -0- P;F 1:2.3

—i—-PZF 111.7
-0- PIF 112.9

-—><-P2'F1;1.1

0 2 4 6 8 10 12
Ageing time (Days)

Fig. 4.47 Variation of swelling index with ageing time of

SBR vulcanizates with resin having different P: F ratios

Fig. 4.47 shows the variation in swelling index. Swelling index decreases as
ageing time increases for all samples indicating progressive crosslinking.
 A101
__
8
filzflzfsré s s _ s _. _ _ _ _ _ _ ,M __.

... ti = *
6. Acetone soluble matter

1 2 awe:-e---o—-so---.~..--as-v--i...--._._;.-i-....-_r-~74-.:.-:=;;_>_~--=-..-=_+‘---._:.-_-=i:-Y- —::_ *:._ - ;~ W;

.121 “i
'1*
_i“
6Aii.»——i—-P:F1:1.7
—I-P:F1:2.3'!
__: 4t -——>(—-P:F1:1.1
0 2 4 6 8 10 12
O i_‘___ ,_. ._., l_ N; _ _ , . g _ n_._ ii

Ageing time (Days)

Fig. 4.48 Variation of acetone soluble matter with ageing time of SBR
vulcanizates with resin having different P: F ratios

Fig. 4.48 shows the variation in acetone soluble matter. Acetone soluble
matter decreases as ageing time increases irrespective of the P: F ratio. Again,
higher gel contents are indicated as ageing proceeds.
4.9.3 Effect of resin content on the ageing properties of miscellaneous
rubbers.

In this study resin with P: F ratio l: 2.9 and CNSL: P ratio 1:1 was used.
It

1.

a. llR
1. Tensile strength

Figs (4.49-4.52) depict the effect of ageing time on the properties of IIR
containing various amounts of the resin.
 Ageing Studies on Rubbers Mq§iifl'ed_By CNSL-PIi_ei:0I- Hexa Resm

14 ~ _~_ ........ _ ~- - ~­ lI
F

oI—\

—0—-R0
\i ii
-—I--R5
;?

——A—R1O
—)(—R15
l

8 ii
3i
ll

1 %K—R2O
—O—R25

4O 2 4s~
6 8~
1Oas
11

12 Ageing time (Days)

Fig. 4.49 Variation of tensile strength with ageing

time of llR vulcanizates with different resin contents

l, i
Referring to Fig. 4.49 before ageing there is a decrease in tensile strength on

‘l Ii
addition of more and more resin. Tensile strength increases for samples having
high resin contents (>1 Sphr).

2. Elongation at break

‘r s?
900 ........._-..-...--....-.._...........-.,..,......- s............-...~-...--......-._.._....t........

i£1
1

-~o—RO
—-I—R5
—A-—R10
—><—R15
0 2 4 6 8 10 12
O

—-x—R20
—0—R25
Ageing time (Days)

Fig. 4.50 Variation of elongation at break with ageing time of

[IR vulcanizates with different resin contents
C‘*Iu1_p£er44)44__g)_*_*gfig)__ 4 __g

Fig. 4.50 shows the effect of ageing time on elongation at break. The
presence of the resin is seen to lower the elongation at break, the effect steadily
increasing on adding more resin. Ageing time has very little effect on the rubben
For higher resin contents there is a steady fall in elongation at break. It is to be
concluded that chemical interaction between the resin and rubber increases and
intercomponent grafting becomes possible as the resin content increases. This

.L
points to some loss of elasticity for samples containing resin as ageing proceeds.

3. Modulus

A'i,—,p~l._.g~_.
"-6-—R0
ll

it

—1 ..—-X-—R20 t —I—R5
f ll —-X-—R15
1 F‘
i _ -0-R25
O 2 4 6 8 10 12 Ageing Time (Days)

Fig. 4.51 Variation of modulus with ageing time of HR vulcanizates with

different resin contents

Fig. 4.51 is a plot of tensile modulus of IIR with ageing time- Maximum tensile
modulus is observed for samples containing the maximum resin (25%). There is a
slight increase in modulus as ageing proceeds. The magnitude of the modulus almost
reaches a constant value at about 7 days and beyond. The slight increase in modulus
during ageing suggests the incorporation of the resin into the crosslinked network. The
presence of the resin causes stiffening of the chain and leads to a higher modulus.
 _ _ s Ageing Swdfe ¢'*_R**!’t1¢:e Medgfisd By _Q1\{5!~+P{“1'*P 1: Hare 8==§='z1

4.Tear strength

A40 \ R0.-.
50 ...._.....................~......................w.. ..............~...._.......~.._.,..,.....,..._....~..... ~......u.............~..~....~...........,..__

it
-- *k**
'*- "'-
.. i*3-—I-—R15——I--R5
—-A-—R10"
-O-I
“-0-—R25
—-ii-—R2O 9

O 2 4 6 8 10 12 Ageing time (days)

Fig. 4.52 Variation of tear strength with ageing time of HR

vulcanizates with different resin contents

Fig. 4.52 shows the effect of ageing time on tear strength of lIR specimens.
The effect of the resin is initially to reduce the tear strength but very soon, after
one day of ageing, all samples show practically the same tear strength. But
beyond that period the tear strength of samples containing the resin shows an
increasing trend, the larger the resin content, the higher being the tear strength.
Tear strength is one property where the presence of resin subsequently improves
the ageing behavior of IIR.

llR has a limited number of unsaturation sites and shows good ageing
characteristics. Even on such a rubber the resin has a very pronounced modifying
action.
h. CR

1. Tensile strength

Figs 4.53-4-56 show the effect of addition of resin on the properties of CR

during ageing.
Qzartsré t t t _ tH C t _ _ C , _ em R

t __ --— ii
1 3 - t‘,M._n.__.te, g..=__ ..sTn,...__t_at..;n-g.:;;.t_L;:;:s;_ns,_ _

C C —l-—R5
g i - __" - i : 5; "-“.*"'RO
X -——)<——R15
i --l——R1O
t

:1
A -at-—-R20 --O-R25

0 2 4 6 8 10 12 Ageing time (Days)

Fig. 4.53 Variation of tensile strength with ageing time of

CR vulcanizates with different resin contents

Fig. 4.53 shows the variation of tensile strength with ageing time of CR
vulcanizates with different resin contents. There is a marginal increase in tensile
strength on addition of resin. It is found that ageing does not affect the tensile
strength of CR substantially. Even in the absence of resin there is very little
reduction in tensile strength after even 10 days of ageing. CR is known to have
good thermal resistance.
 K _ Ageing Studies 9'! R)‘_b?’*"f$ M9¢=§fi§d_ 81¢"? P-!"5@'10k Hex“ Resin

2. Elongation at break

....... ..... ....... .......... My ......... -..,..-._.............,......._.-..-..w.-.-------------..,..,...._- ............ N, ................. .. Y

ti

41%

—-O-—R0
—I-—R5
A “1'Q;\. —-A-R10
—-X-—R15

._ i “‘\‘ lliiii
—-Q
1
--X——R2O
—-O-—R25
ll

O 2 4 6 8 10 12 l
I

0 ‘L,_,-~ ;,, ,-a T ;, 1 ,--~_, _' _-, ~, I ~ ,' W , ~ V’; ~-- ,'~ ,~ _ __, ~_,-'1”,--_,, 3

Ageing time (Days)

Fig. 4.54 Variation of elongation at break with ageing

time of CR vulcanizates with different resin contents

Fig. 4.54 shows that elongation at break falls drastically on continuous

ageing. The samples containing resin has a comparatively lower elongation at
break after ageing. This shows stiffening of the network and possibly incorporation
of the resin into the crosslinked network.
9'mr1*e:-4i____-._-___
3. Modulus

10 .\ _.
t‘*—+—RO
‘l

‘
—-it-—R 10
- t ——x——R15
13
...... ­
‘—X—'R20:&
1,
I.

—.-—R25

O 2 4 6 8 10 12 Ageing Time (Days)

Fig. 4.55 Variation of modulus with ageing time of CR vulcanizates with

different resin contents

Fig. 4.55 shows that there is initially an increase in tensile modulus on

addition of resin. All the samples including the one not containing the resin show
an increase in modulus as ageing proceeds. Change in modulus on ageing can be
the result of chemical changes like dehydrochlorination and interaction between the
rubber and resin.
 Ageing Studies 011 Rubbers Modified By CNSL-Pllcnol- Hexa Resin

4. Tear strength

100

e-
.§
90 ___ RO
80 ___ R5
~
s: 70 _ _ R10
C,
c _ _ R15
60 l----.;:;
e
"in
~
~
~
I-
50
40
- ___ R20
_ _ R25

30
0 2 4 6 8 10 12
Ageing time (Days)

Fig, 4.56 Variation of tear strength with ageing time of CR

vulcanizates with different resin contents

Fig. 4.56 is a plot of tear strength with ageing time. CR containing resin has
superior tear strength at all stages of the study. Fall in tear strength with ageing
time is very moderate.

c. EPDM

Figs 4.57-4.59 show the effect of ageing time on the properties of EPDM
containing resin.

1. Tensile strength

___ RO
___ R5
_ _ R10
_ _ R15
___ R20
_ _ R25

0'---------------'
o 2 4 6 B 10
Ageing time (Days)

Fig. 4.57 Variation of tensile strength with ageing time of

EPDM vulcanizates with different resin contents

175
Qhflrfsréo a a _ _ a _ o _ _ ag _ _ _
Fig. 4.57 shows a reduction in tensile strength on addition of resin. All the
samples containing resin show almost constant tensile strength on ageing. EPDM
has considerable age resistance. The resin is seen to stabilize the tensile strength.

990 .
.l% 1‘ Yfi
2. Elongation at break

800

-100 .i
\-‘wg
200i. itif '
1
‘*'- 1*-—I-—R5
1;
—A——R10
— ale _ —-X-—R15
—-alt-—R20
*1 ——O— R 25
O 2 4 6 8 10 12
Ageing time (Days)
I:

‘i

ti
-x
1.
-0-R0

Fig. 4.58 Variation of elongation at break with ageing time of

EPDM vulcanizates with different resin contents

Fig. 4.58 shows fall in elongation at break on ageing. All samples shows
steady reduction in elongation at break on ageing, although elongation at break for
samples containing the resin is less at any stage of the ageing process- The resin
causes a stiffening of the network without any apparent interaction between the
resin and rubber.
_ _ _ 7 Ageing Studies or] Rrfhbershilofiificfl By Cl§i_SLi-I’:I1_£iIl1;)l:f'|lP;?£fl itefilt

3. Modulus

4.5 -_> - _ - 7,; A - -_»_-_-_--_-_-=.-=_-= _-_-;:;- -.-.4--_-.7.-___— —_—.-.-_- —_ -7- — -.—_ .1 -_—_-_-_—_—_ -_- »_-_- — ~ - -1». ,—_— V - 1 -_ ,—; -_?- -_~_'_‘_+.-_-.-_'_¢-;-_-_-.7 »\D\ »_-_-.-_-_?_-_»_-_-.7 . =-—.—=.—.-_=_ .-=.—.-_;—=»_'.».- @~ , -­

4.
A 3.5 --0-—RO
3 5
-—I—-R5
Q} 2.5 --A-—-R10
-Q 2 ——)(-—R15
——X-—R2O
1 --O-—R25
0.5
O Liieii.
O 2 4 6 8e10 of
12
»
<
1

Ageing Time (Days)

Fig. 4.59 Variation of modulus with ageing time of EPDM

vulcanizates with different resin contents

Fig. 4.59 is a plot of tensile modulus versus ageing time of EPDM lhere is
a general increase in modulus with ageing time. Samples containing resin have a
lower modulus at all stages of the study. Again lack of interaction between resin
and mbber is indicated.

4. Tear strength
~.-,....,..»»--».-...>.\....,..,....,........_...-~..... ».....\.....»-,.-.-.._-_-..~...,..........,-..\. -..,.......»-.-...~.....,-~~»--- - /--.,-~..-..,- -..-...,,-.......»......,.,--v.

I
Y

i
-0-R0
Xi 5 —I—R5
i

—-Q--R10
t
-—X—R15
-—X-—R2O
i

i
( —O-—R25
i

0 2 4 6 8 10 12
S

0 -,__ _ —, '~1 *4-'—,'—:.~~—e. —.--—>. _—*-I-. '_,, _, ;,~; _'__~;_ 41"!i

Ageing Time (Days)

Fig. 4.60 Variation of tear strength with ageing time of

EPDM vulcanizates with different resin contents
.7 __ _ _ _ 7 _ _ *_ if
Chapter 4

Fig. 4.60 shows the change in tear strength with ageing time. Samples
containing resin in excess of 10% show an increase in tear strength with ageing time
while samples with low resin content show a slight fall in tear strength on ageing. At
about 8 days of ageing all samples have practically the same tear strength. The tear
strength of samples with higher resin content continues to rise even afier that.

d. NR

1. Tensile strength

»-\ 25 0
.1 llit1
+R 0
30 -.___a_..-_.i...-:,.._ _.,~.._,,...,__,.._.:m.,s_...... __sa_._s.t=£

i.
ll

:i
l.

—I—-R5

.; —x-R15
= T; _Ii:\ it —-X-R20
1 —t—-R10

0
Og2g___
4 6 8_..._
10_. 12
_.
Ageing Time (Days)

Fig. 4.6] Variation of tensile strength with ageing time of

NR vulcanizates with different resin contents

Fig. 4.61 shows the variation of tensile strength with ageing time for NR
samples. Initially the presence of the resin leads to a high tensile strength. But all
the samples show a steep fall in tensile strength on continued ageing. Towards
later stages of ageing all the curves come closer. NR is known to undergo chain
scission on prolonged periods of ageing. The extent to which this is prevented by
the resin is not substantial. Hence this resin cannot be considered as a good
ageing modifier for NR.
 Ageing Studies 01/ Rubbers Modified By CNSL-Pllellol- Hexa Resin

2. Elongation at break

900
?1 800 ___ RO
:; 700
~ ____ R 5
e
.c
600
_ 500 _ _ R10
~

c:: 400 ___ R 15

~ ~~~~~~~
---ll- R 20
g' 200 ---+-R25
~ 300
100
o
o 2 4 6 8 10 12
Ageing time (Days)

Fig. 4.62 Variation of elongation at break with ageing time

of NR vukanizates with different resin contents

Fig. 4.62 shows a higher elongation at break for samples containing resin. As
in the case of tensile strength there is a steep fall in elongation at break on ageing.
The initial high elongation at break of samples containing large amounts of resin
falls sharply until at about 8 days of ageing time. The curves almost overlap each
other at this stage. The resin is not very effective on prolonged ageing.

3. Modulus

6 ___ Ra
ro5 ____ R 5

l~~~§~~~::~::=:~
:;; 4 _ _ RlO

"! 3 ___ R 15
~
u, 2 ---ll- R 20
:;; 1
---+-R25
o
o 2 4 6 8 10 12
Ageing time (Days)

Fig. 4.63 Variation of modulus with ageing time

of NR vulcanizates with different resin contents

179
§'1“a**:r4..i_.__i..______ sh
Fig. 4.63 shows the variation of modulus on incorporation of resin. Samples
containing high amounts of resin show an increase in modulus on ageing while
those containing little or no resin show a gradual fall in modulus. This can be

80
90 l
Tl
attributed to the physical presence of resin in the nibber network.

4. Tear strength

1 O0 __....._...._...;a,.;.._.i_..__._.c£s_.-.a,sq.-.._..._...-..........~.........--_.........__..._......_.-,._....__..._...__

60 --I-— R 5
70 t - 1 -§o—'iR O
-x- R 15
40
50
ii
20
H1?
@­
30 gt -—*—— Y
--I"-' R
R
10
" -Q-" R 25
‘l
20
10

0 2 4 6 8 10 12 Ageing time (Days)

Fig. 4.64 Variation of tear strength with ageing time of NR vulcanizates with
different resin contents

Fig. 4.64 shows the effect of ageing time on tear strength. Initially high tear
strength is obsen/ed for samples with high resin content. But towards the later
stages of ageing the curves come closer although slightly better retention of tear
strength is observed in the case of samples cont.aining high amounts of resin. In
general, the resin is not able to prevent fall in most properties on ageing.
_ g c Ageing Shim? P?‘ R1'l2b_"§ £"94?fi§4 1221 ¢1§'5_l;P£~:"<_": 1i@2<“_Rs$i3'

4.10 CONCLUSIONS

The copolymer obtained by condensation of phenol and CNSL with

hexamethylenetetramine improves the ageing characteristics of NBR with respect
to retention of tensile strength, modulus, tear strength and elongation at break when
the resin content is more than l5 phr. Vulcanizates containing resin with a P: F
mole ratio l:2.9 showed the least change in properties on ageing. As the relative
amounts of formaldehyde in the resin decreased, the rubber showed increases in
tensile strength, tensile modulus and tear strength on ageing. The effect of CNSL
was less noticeable than that of phenol. But the addition of CNSL still resulted in
substantial improvement in ageing characteristics. Considering the low cost of
CNSL and its renewable nature, partial replacement of phenol with CNSL has
practical significance.

CNSL improves the ageing characteristics of SBR with respect to tensile

strength, modulus, tear strength and elongation at break, when subjected to ageing
up to l0 days at 1000C. At l5% CNSL, property retention is very high especially in
the case of tensile strength, modulus and tear strength. Similarly the resin
synthesized from CNSL, phenol and formaldehyde shows very good age modifying
properties. In the case of the resin, again, the best results are noticed in the case of
tensile strength and tear strength. From the property retention viewpoint about l5%
resin is found to be very effective. Vulcanizate containing resin with P: F ratio
l:2.9 showed the least change in properties. The resin is more effective as age
resistor than the oil. Tensile strength, modulus and tear strength increases are
noticed on ageing.

In the case of IIR the presence of resin leads to reduction in tensile strength,
elongation at break and tear strength. llR shows good ageing properties with resin
content above l0 phr.

CR has good inherent resistance to ageing. A marginal increase in tensile

strength on addition of resin is retained throughout the ageing period. Tear strength
and modulus also show an increase on ageing. The presence of resin does not alter
this behavior. The elongation at break reduced on addition of resin and continues to
fall on ageing.
Chapter i
Tensile strength, elongation at break, modulus and tear strength of EPDM
are found to decrease on addition of resin. Although the samples show good
property retention on ageing the use of the resin may not be desirable because of
the fall in properties on adding it.

A continuous fall in tensile strength, elongation at break and tear strength in

the case of NR is not stopped by the presence of the resin. But initial values of
these properties before ageing improve marginally on addition of resin. Only
modulus retains/improves the original magnitude on ageing. The presence of resin
does not alter this behavior. The use of resin may not be desirable in this case also.
- - - Ageing Sriidiee P.".R*sbb¢r§M0,d2fi§4 By £N€£:B*1@!'9': Bee? £5!"

REFERENCES
1. E.H. Bevilacqua , J. Appl. Polymer Sci., 10,1925 (1966)
2. J.l... Cunnen , Rubber Chem. T echno1., 41,182 (1968)
3. J.R. Shelton, Rubber Chem. Techno] 56, G71 (1983)
4. P.M. Norling, T.C.P Lee and A.V Tobolsky, Rubber Chem. Techno1., 38,
1198(1965)
5. R.G. Bauman and S.H Maron, J. Po1ym.Sci., 22, 203 (1956)
6. J.P. Berry and W.F. Watson, J Polym. Sci., 18, 201 (1955)
7. R.W. Keller, Rubber Chem. Teehnol, 58, 637 (1985)
8. .1.L. Morand, Rubber Chem. Techno1., 50, 3'/3(1977)
9. J.R. Shelton, Rubber Chem. Tcchno1., 30, 1251 (1957)
10. Bevilacqua and W.J. Wenisch, J.App1.Po1m. Sci., 9, 267 (1965)
l1. M.Porter, The Chemistry of Sulfides, A.V. Toboisky ed., lnterscience
publishers, New York ( 1968).
12. 1.. Bateman, The Chemistry and Physics of Rubber-like Substances, Me Laren
and Sons Ltd., London (1963).
13. T.H. Kuran, Rubber World, 192, 20, (1985)
14. A.Y. Conm, Science and Technology of Rubber, F.R Enrich (ed). Academic
Press, New York, (1978).
15. L.Slusarsl<i, G.Janowska, J.Therm. Anal. , 30, 1 105 (1986).
16. T.O. Skinner and A Awabon , Rubber Age, 99 (1 1), 76 (1961_)
17. R.N. Datte , J.H Wilbrink and F.A Ingham. lndian Rubber J., 8, 52 (1994)
18. J.C. Searer, Rubber Age, 62,191(1947)
19. R.P. Lattimer, R.A Kinsey and R.W. Layer, Rubber Chem. Techno1., 62, 107
(1982)
20. M. Morton, Rubber Technology, Chapman & Hall, (1995).
21. ASTM D 3187-0()(2004)
22. ASTM D 3185-99
23. ASTM D 3188-O0
§h‘!P*€"§_._2__ 1__ _
24. ASTM D 3190-00
25. ASTM D 3568-03
26. ASTM D 3184-89
27. ASTM D 573-88
28. ASTM D 412-98 a
29. ASTM D 624-00
30. ASTM D 395-03
31. ASTM D 676-86
32. DIN 53516
33. ASTM D 3616-95
34. ASTM D 297-93
35- S. Van der Meer, Rec. Trav. Chem., 63, 147 (1944)
36. A. Knop, W. Scheib, Chemistry and Applications of Phenolic Resins,
Springer Verlag, New York (1979)
37. A.R.R. Menon, C.K.S. Pillai and G.B. Nando,, Journal of Applied Polymer
Science, 68, 1303-1311(1998)
38. A.R.R. Menon, C.K.S. Pillai and G.B- Nand0,, Polymer 39(17), 4033-4036
(1998)
39. A.R.R. Menon, C.K.S. Pillai and G.B. Nando,, Joumal of Applied Polymer
Science, 51 (13), 2157 (1994)
40. A.R.R. Menon, C.K.S. Pillai and G.B. Nando,, Kauts.. Gummi Kunsts 45 (9),
708 (1992)
Chapter 5
DEVELOPMENT OF PARTICLEBOARD
5.1 INTRODUCTION
5.2 EXPERIMENTAL
5.2.1 Moulds and other accessories
5.2.2 Moulding procedure
5.3 MOULDING OF PARTICLEBOARD
5.3.1 Particleboard from CNSL — hexa reactive mixture (Case 1)
a. Ingredients
1. Binder
2. Filler
3. Additives
b. Formulation
c. Moulding parameters
I. Cure temperature
2. Cure time
3. Curing pressure
4. Resin content
5. P: F ratio
6. CNSL: P ratio
5.3.2 Particleboard from dry moulding powder (Case 2)
a. Ingredients
I. Binder.
2. Fillers
3. Additives
b. Formulation
c. Moulding parameters
I. Resin come";
C hagter 5

2. P: F ratio
3. CNSL: P ratio
5.4 TESTING OF PARTICLEBOARD
a. Density
b. Moisture content
c. Water absorption
d. Tensile strength parallel to surface.
e. Tensile strength perpendicular to face (Internal bond strength)
f. Static bending tests
g. Compressibility
5.5 RESULTS AND DISCUSSION
5.5.] Effect of moulding conditions and stoichiometry on the
properties of particleboard from CNSL-hexa reactive resin
(Case 1).
a. Effect of cure temperature
b. Effect of cure time
c. Effect of curing pressure
d. Effect of resin content
e. Effect of P: F ratio
f. Effect of CNSL: P ratio
5.5.2 Effect of moulding conditions and stoichiometry on the
properties of particleboard from CNSL-phenol-hexa copolymer
(Case 2)
a. Effect of resin content
b. Effect of P: F ratio
c. Effect of CNSL: P ratio
5.5.3 Effect of fillers
5.6 CONCLUSIONS
REFERENCES
 Development of Particleboard

DEVELOPMENT OF PARTICLEBOARD

5.1 INTRODUCTION

Particleboards were first made during the l930’s. The wood particleboard
industry evolved due to shortage of timber and the need to dispose of large
quantities of sawdust, planar shavings and to a lesser extent, mill residues and other
relatively homogeneous waste material produced by other wood industries. They
are widely used because they enable wood particles from relatively useless small
size and/or low grade timber to be transformed into useful large wooden panels (1).

Properties of the board depend among other things on the kind and amount
of binder used. When phenolic resins are used as binders particleboards are
characterized by good physical and mechanical properties.

Particleboards are manufactured from particles of wood or other

lignocellulose material, formed and pressed together by the use of an organic
binder with the help of one or more of agents, such as heat, pressure, catalyst etc
(2). The basic material from which particleboards are made are (a) chips, which are
wood particles typically used in pulp manufacture (b) flakes, which are
mechanically sliced wood particles (c) ribbons, wood particles of specific thickness
but varied length (d) shavings, thin, of short length and consisting of ruptured
fibers (e) splinters, wood particles greater in length compared to width and (D
sawdust, comparable to particulate fillers but still possessing fibrous structure.
Particleboard retains many of the properties of the wood from which it is made.

Particleboards for construction must have high strength and weather

resistance. The specific gravity of particleboard may be affected by production
parameters like chip form, and reactivity of the resin. Bond strength depends on
chip form and binder content.

For special applications, the properties of the boards may be modified by the
addition of Chemical agents to provide additional properties such as high
compressive strength, water resistance, fire resistance and resistance to decay or
insect attack.
Chapter 5

The largest use of these panels is in the building industry, in which they
serve to cover up space — on walls, floors and ceilings. In this application, they may
serve various functions- heat insulation, sound insulation etc. They are also widely
used in the manufacture of fumiture, floor underlayment, cabinets, in home
construction and, a significant amount, in the manufacture of automobiles.

Sawdust is recommended as filler for its relatively low specific weight and
its abundance as a cheap byproduct in wood workshops. Agricultural wastes such
as rice husk, cotton husk, coconut husk etc. can be used for making particleboards
that would replace wood products (3-9).

Cost of these boards remains high due to the high cost of the synthetic resin.
Natural resin such as that based on CNSL can replace synthetic resins in board
manufacture. Application of CNSL as a full or partial replacement for synthetic
resin may be of interest in these days of diminishing petroleum resources.

In this study particleboards based on sawdust and CNSL were prepared and
the physical and mechanical properties determined for various synthesis and
moulding conditions.

5.2 EXPERIMENTAL

This section presents the experimental details of the developmental work on

particleboard made from CNSL. Two methods were adopted for the moulding of
particleboard.
a. Board made from CNSL- hexa reactive mixture
b. Board made from CNSL- phenol-hexa copolymer resin
Sections 5.2.1 and 5.2.2 discuss details of mould design and moulding
procedure common to both cases. Specific details of each moulding procedure are
given in Sections 5.3.1 and 5.3.2.

5.2.1 Moulds and other accessories

The mold is made from mild steel and is a specially designed three piece
assembly. The bottom plate and the top plate are separated by a spacer/ frame
which holds the mold charge prior to molding. The top plate has a punch that

188
 Development of Particleboard

engages the frame. The punch when pressed by the platen compresses the powder
to about one third of its original thickness. The frame has a taper for easy release of
the moulded product. Photographs of the mould are given below. The mould is
designed for a board of size 300x 300 x 10 mm.

2M _;~.;...-2-;-1 2.

Fig. 5.1 Three piece mould for particleboard

5.2.2 Moulding procedure

The mould was heated to moulding temperature pn'or to molding. The

moulding composition was then charged. In order to facilitate easy release of the
molding cellophane sheets were kept on both sides of the mould charge. The mould

189
Chapter 5 g

with the molding composition was placed in a hydraulic press and the required
pressure applied. Degassing was done at every five minutes to avoid blisters. After
curing, the mould was Opened and allowed to cool. The product was then taken out
from the mould. A board with dimensions 300x300xl0 mm was obtained.

5.3 MOULDING OF PARTICLEBOARD

5.3.1 Particleboard from CNSL-hexa reactive mixture (Case 1).

a. Ingredients
I. Binder

A reactive CNSL formaldehyde resin served as binder. CNSL and hexa were
heated at 100°C for 30 minutes in a beaker with continuous stirring. This resin was
used for moulding particleboard to study the effect of cure temperature, cure time,
curing pressure, resin content and P: F ratio. To study the effect of CNSL: P ratio,
resin was prepared by heating mixtures of CNSL, phenol and hexa in different
proportions.

Z. Filler

Sawdust collected from saw mills. Sawdust contains wood chips of varying
sizes from fine dust to pieces as long as 0.5 cm.

3. Additives

l. Magnesium oxide catalyst to speed up the curing reaction.

2. Dimethyl forrnamide as accelerator.
3. Zinc stearate as lubricant.
4. Naphthalene improve flow properties

b. Formulation
Sawdust 100
Resin 5-25 %
MgO 0.1- 0.5 %
Zinc stearate l °/0
Naphthalene 005- 0-25 %
Dimethyl formamide 005- 0-25 %
 Development of Particleboard

c. Moulding parameters
Particleboards were made for different values of the following variables

1. Cure temperature
Keeping resin content constant at 15%, cure time 15 minutes, curing
pressure 13.72 MPa, P: F ratio 112.9 and CNSL: P ratio 1:1, cure temperature was
varied as 150. 160, 170, 180 and 190"c
2. Cure time

Keeping cure temperature constant at 150°C, resin content 15%, curing

pressure13.72 MPa, P: F ratio 1:2.9 and CNSL: P ratio 1:1, cure time was varied as
5, 10, 15, 20 and 25 minutes.

3. Curing pressure
Keeping resin content constant at 15%, cure temperature 150°C, cure time 15
minutes, P: F ratio 1:2.9 and CNSL: P ratio 1:1, cure pressure was varied as 3.43,
6.86, 10.78 and 13.72 MPa.
4. Resin content

Keeping cure temperature constant at 150°C, cure time 15 minutes, curing

pressure 13.72 MPa, P: F ratio 112.9 and CNSL: P ratio 1:1, resin content was
varied as 5, 10, 15, 20 and 25 phr
5. P: F ratio

Keeping resin content constant at 15%, cure temperature 1509C, cure time 15
minutes, curing pressure13.72 MPa, and CNSL: P ratio 1:1, P: F ratio was varied as
1:1.1,1:1.7,1:2.3 and 1:2.9
6. CNSL: P ratio

Keeping resin content constant at 15%, cure temperature 150°C, cure time 15
minutes, curing pressure 13.72 MPa and P: F ratio 112.9. CNSL: P ratio was varied
as 100:0. 75:25, 50:50, 25:75 and 0:100.

Table 5.1 summarizes the moulding parameters maintained for particleboard

moulding.
 ghapter 5? _ _ _ j _ _ 7

H _ 150
150
160
170
180
190

150
11
_.|~— — _

1 15
1 15
1 15
1 15
W5
10
15
Table 5.1
Moulding parameters used for particleboard with reactive
CNSL- hexa resin as binder
Moulding parameters
‘T {Cure 5 71 5 Curing 7 1 7 7 717 7 5 it 7. 5 71
1 t t Y Cqetlme re‘sure 1 Resm P:Fratio 1 CNSLP
emI()<1g; we .1 (mmutes)
MP8.
1 15 1 ' 1 "1
1 P S 1 content \ 1 ratlo A
13.72
13.72
13.72
13.72

13.72
13.72
7 15
112.9
112.9
112.9
112.9
112.9
112.9
112.9
_.1_
100:0 N
10010 1
100:0 .
100:0 W
100:0 V
100:0 5
100:0
3

150 15 13.72 112.9 100:0 ‘A

150 20 13.72 112.9 100;0 ,.
150 13.72 112.9
lE7__25
[_ 150 . 15 3.43 1
1

112.9
100:0 4.
1500107 1
150
150
, 15 15
6.86
10.78
112.9
112.9
100:0 .
10010 Y
1_. _ 150 1 15 13.72 112.9 100:0 1
1

150 * 15 1

13.72 112.9 :1 *100:0

"‘1
150 ‘ 15 13.72 112.9 100:0 ‘1
150 A 15 13.72 112.9 100:0 1
1 15 100;0
150
150 15
1. 1
T
13.72
13.72
112.9
112.9 100:0 1
,,,_ -9 11
100:0 ‘
150
15
717‘ 715 13.72 112.9
1

150 13.72 112.3 100:0 1

150 1 15 13.72 111.7 100:0 1
150 115 13.72 111.1
10010 p
W­ 150 715 13.72 1 112.9 100:0
150 15 13.72 112.9 75:25
150 15 13.72 112.9 50:50 1
150 15 13.72 112.9 25.75 1.
150 115 13.72 _1 ‘1
112.9
1

1 4
01100 1
 Development of Particleboard

5.3.2 Particleboard from dry moulding powder (Case 2)

a. Ingredients
I. Binder.

A dry moulding powder composition based on phenol-CNSL-hexa

copolymer was prepared. Details are given in Section 2.3

2. Fillers
l. Sawdust — collected from sawmills
2. Rice husk —collected from rice mills.

3. Additives
l. Magnesium oxide catalyst to speed up the curing reaction.
2. Dimethyl formamide as accelerator.
Zinc stearate as lubricant.
Naphthalene improve flow properties.
h. Formulation
Sawdust l0O
Resin 5-25 %
M gO 0.1- 0.5%
Zinc stearate l %
Naphthalene 0.05- 0.25%
Dimethyl formamide 0.05- 0.25%
c. Moulding parameters
l. Resin content

Keeping cure temperature constant at 1500C, cure time 15 minutes, curing

pressure 13.72 MPa , P: F ratio 1:2!) and CNSL: P ratio 1:1, resin content was
varied as 5, 10, l5, 20 and 25 phr
¢'1s=P€¢r5___ _ _ ,2 _,
2. P: F ratio

Keeping resin content constant at 15%, cure temperature 150°C, cure time 15
minutes, curing pressure 13.72 MPa_, and CNSL: P ratio 1:1, P: F ratio was varied
1:1.1,1:1.7,1:2.3 and 112.9

3. CNSL: P ratio

Keeping resin content constant at 15%, cure temperature 150°C, cure time 15
minutes, curing pressure 13.72 MPa, P: F ratio 112.9 and CNSL: P ratio 1:1, CNSL:
P ratio was varied as 100:0, 75:25, 50:50, 25:75 and 0:100.
Table 5.2
Moulding parameters used for moulding particleboard with
CNSl,- phenol-hexa resin as bin¢ler(M0u1ding temperature =1 500 C, cure
time = 15 minutes, Moulding pressure = 13.72 MPa)

7 liesff 7 P: F5113 T E"1~1si:i> 7

content 1 ratio 1
,5
1
1

, ,11 7 '—'1
1
l:2.9
10 501750: 7 1
1

1:2.9 50;50
15 1 1:2.9

20
25
1:2.9
1:2.9
50:50
50I5O 1
L 1; 1; C 11,
15 1 1:2.9 50:50 1

1 115
5‘
15 1‘

: _; : T ,
112.3
111.7
1:1.1
i1
50:50
50:50 1

15
to 1
W:
151 1:2.9 1 160:0‘ 1
112.9 75125
' 15 "
1

l:2.9

15
1

50:50 1
1

1
1 15 1 1:2.9 25275 1
l:2.9
,1
0:100 1
g _ f _ g _ _ _ _ _ _ *D£’iZIfl’TQ]Z713£’_{Il"0I]3d!'ffC{8t?0fIf£i

5.4 TESTING OF PARTICLEBOARD

(AS PER IS 2380-1977 (10))

a. Density
The specimen used was of 7.5 cm wide and 15 cm long.
Density = mass of the specimen in gm / {length (cm) x width (cm) x
thickness (cm)} g/cm‘;

b. Moisture content
The specimen used was of 7.5 cm wide and 15 cm long. It was then dried in
an oven at 103°C until the mass was constant. The moisture content, expressed as
percentage of oven dry mass, was calculated
Moisture content = (M, —M0)/MU X l00
M, --~ initial mass
M0 — oven dry mass

c. Water absorption

Test specimen used was 30 X 30 cm size. After conditioning the specimen

was weighed and the width, length and thickness measured. The specimen was then
submerged horizontally in clean water maintained at a temperature of 27°C. The
test specimens were separated by at least l5mm from each other and from the
bottom and sides of the container. After a 24 hours submersion, the specimen was
suspended to drain for 10 minutes, at the end of which the excess water was
removed and the specimen was immediately weighed. The amount of water
absorbed was calculated from the increase in mass of the specimen and the water
absorption was expressed as percentage by mass alter conditioning.

d. Tensile strength parallel to the surface

Tensile strength in the parallel- to- face orientation is the resistance of a

board material when pulled apart parallel to its surface. Tensile strength parallel to
the surface is the load at the time of fracture divided by the cross sectional area
(width x thickness) of the specimen.
 _ ..~___ 7 _ V
Chapter 5

l - length of specimen, mm

f. Static bending tests

Static bending tests determine both modulus of rupture (MOR) and modulus
of elasticity (MOE) of composites. Universal Testing Machine was used for
measuring these properties. Samples of 300 mm length, l0mm thickness and 50
mm width were used. The test was conducted at a crosshead speed of 6 mm/min
and loading span used was 240 mm.

I. Modulus of rupture (MOR)

Modulus of rupture is the ultimate bending stress of a material in flexure or

bending and it is frequently used in comparing one material to another.
MOR = 3PL/2bd2.
MOR - Modulus of mpture, MPa.
P - maximum bending load, N.
L - length of span, mm, 24x thickness.
b - width of specimen, mm.
d - thickness of specimen, mm.
2. .M0dulus of elasticity (MOE)

Modulus of elasticity is determined from the slope of the straight line portion
ofthe load-deflection curve (P,/Y1).
MOE = P,L3/4bd3Y,
MOE - stiffness (apparent modulus of elasticity), MPa
Pl - load at proportion limit, N
L - length of span, mm, 24x thickness.
b - width of specimen, mm
d - thickness of specimen, mm
Yl - centre deflection at proportional limit, mm
A typical load-deflection curve (particleboard moulded with sawdust and
CNSL- phenol ~ hexa eopolymer resin with P: F ratio l:2.9, CNSL: P ratio l:l and
resin content 25 %) is shown in Fig.5.3
 40 1‘ ~
120 +1
A 100
so ;i
so
20 <7

g. Compressibility
e Load- deflection curve

0 i»._ , _ .__ .. e ..-.._..__._ 4 -.—‘L*—‘;=:

O 0.2 0.4 0.6 0.8 1
Fig. 5.4 Load deflection curve for particleboard
Stroke strain (°/i)

The test specimen used was 50 X 50 X 50 mm. The specimen was prepared
by gluing five pieces of the board face to face. The size of the specimen was
measured correct to 0.1 mm and mass correct to 0.01 g. The test was carried out at
room temperature. The specimen was placed horizontally on the platform of the
machine in flat position. The load was applied vertically on the specimen, at a
constant rate ofloading of 0.6 mm/minute.

Initially a load of l0 Kg was given on the specimen and taken as zero

position. Then a load of 500 Kg was applied and this load was maintained for 10
minutes. The defonnation was measured alter 10 minutes and was recorded as the
value of compressibility.
Development of Particleboard

,.._._..................,.......,......................-.._...-...........__..........-................--.....-..,. .............-...... .... ­

l

5.5 RESULTS AND DISCUSSION

Wood particles consist of cellulose, hemi cellulose, lignin and substances

like resins, oils etc. Lignin is highly polymeric substance with a phenolic structure
(ll). Most abundant chemical sites in the wood cell wall polymers are hydroxyl
groups (l2)
The sawdust used is predominantly of rosewood. Components of rosewood
are geraniol, linalool_ nerol, lineole, terpinol, dipentene (13) in addition to
cellulose, lignin etc.

Sawdust contain several reactive compounds and functional groups, so that

"*"\"l1't from hvdrogen bond formation, a number of chemical reactions with phenol­
§'1eP£"§___,_,lt_l_l,_s _lls
fonnaldehyde condensate products can occur (2). The following types of reactions
are believed to occur (14). l) hydrogen bonds fomi between hydroxyl groups of
cellulose and phenolic resin, 2) crosslinking can take place between wood cell wall
hydroxyls and formaldehyde and 3) crosslinks take place between the hydroxyl
groups on the same or different cellulose, hemi cellulose and lignin polymers. T0
what extent these three interactions take place is a matter of conjecture.
This section presents the results of various studies relating to the
development of particleboards. These results can be divided into two broad
categories.
a. Particleboard from CNSL- hexa reactive mixture (Case I) and
b. Particleboards flom dry moulding powder consisting of CNSI-phen0I- hexa
copolymer (Case 2)
5.5.1. Effect of moulding conditions and stoichiometry on the properties of
particleboard from CNSL-hexa reactive resin (Case 1)
a. Effect of cure temperature
To study the effect of cure temperature on the properties of particleboard,
boards were made with resin content l5 phr, curing pressure 13.42 MPa, cure time
15 minutes, P: F ratio 112.9 and CNSL: P ratio 100: 0 and varying cure
temperatures.
 Development of Particieboard

-- at
it %Ԥ * ii *1
4 ‘F k%ma—___.

O
== esereeefles — e e »—-—.—-e—*><~_ e - fix
150 160 170 180 190 200
Cure temperature (OC)

-+— Density (Kg/m3) —-I—~ Moisture content (%) ——-A—— T.S(parallel)

-><- T.S(perpendicular) --x- Compressibility(mm)

Fig. 5.5 Variation of properties of the particleboard

(Case 1) as a function of cure temperature

Fig. 5.5 shows the variation in density, moisture content, tensile strength
(parallel), tensile strength (perpendicular) and compressibility with cure
temperature.

Density is almost constant when the cure temperature changes from 150 to
190°C.

The effect of cure temperature on the moisture content of the resin is not
substantial.

Tensile strength (parallel-to- face orientation) is the resistance of a board

material when pulled apart parallel to its surface. lt is the maximum load a
specimen can withstand when subjected to tensile loads in the direction of the
length. The board shows maximum tensile strength at 160°C. Tensile strength
(parallel) is seen to slightly decrease at high cure temperature. This may be due to
Ch¢'~'r1*<'§____._ ,_ s C ___ __ slog g s U C ,__

degradation of wood fibers and also the negative effect on the properties of the
resin binder.

Tensile strength perpendicular to face is a measure of the resistance of a

'§i
material when pulled apart in the direction perpendicular to its surface. This test is
a true measure of the adhesive / bonding strength of the resin. The stress is applied
on a comparatively large area resulting in failure along a section parallel to both
faces. Particleboard shows maximum tensile strength (perpendicular) at 150°C.
Above this temperature bonding strength decreases. This can be due to possible
degradation of fiber or resin. At high temperatures water is eliminated between
cellulose hydroxyl groups to form ether bonds (ll). Ether bonds are not as
amenable as hydroxyl groups to hydrogen bonding with polar phenolic resin. At
higher temperatures exudation of extractives to the surface as well as closure of
micro pores in cell walls occurs, which reduces the number of active sites for
bonding.

Compressibility is almost constant when the cure temperature changes from

150 to 180°C. From 180 to 1900C there is a sudden decrease in compressibility. It
is likely that above 180°C the resin becomes too rigid and the board reaches a state
of maximum compaction. Hence compressibility falls at this stage.

404? --*~ L
‘**-~_-. ? i
50 .....__.....-..--.........._-.._...._........_.......-.....__-._.....--._.._....-_.*.-...._.,_.-........_..._.._..-......_.....-.._....._......_....----..__.. - .. - ­

1O\ '”“‘” .__._____ _4__. Q

150 160 170 180 190 200
Cure temperature (99)

-o- Water absorption (%) -—I— MOR(MPa)

Fig. 5.6 Variation of properties of the particleboard
(Case 1) as a function of cure ‘|'DIr\r\n--—*
 I
Fig. 5.6 shows the variation in water absorption and MOR with cure
temperature.

At high curing temperatures water absorption decreases. At higher

temperatures, a more crosslinked and impenetrable board results.

MOR is a measurement of composite board bending strength. MOR is the

ultimate bending stress of the material in bending and it is frequently used in
comparing one material to another. Maximum MOR is obtained at 150°C which
matches the performance required by the Indian Standards. Further increase in cure
temperature decreases MOR.

1000 ‘._......._..._ ._ ....-.._...._ .. .~ ......_~._.........._..,_.u._...._...._..._..._.....

l if-':_-‘_7* 7 7;‘? _*_‘_—;-_‘e_ -_ *‘. i

lk/.,
Development of Particleboard

_~...,.__.».-_.,-.i~t--... ..i.A\-._.\~.-?,.”---..~.-ta-._ :¢..._..~.-.......i~.__., ‘Q,-,..--A--.i, t-i vi.“-_._.-._.,~,-._ ,--1,--...._ -m...--__~,.i.-,_.--i-_.. -..__-._~--?~

Fig. 5.7 Variation of MOE of the particleboard

(Case 1) as a function of cure temperature

Fig. 5.7 shows the variation in MOE with cure temperature. MOE is
practically unaffected by cure temperature.

b. Effect of cure time

Cure temperature (OC)

To study the effect of cure time on the properties of particleboard,

particleboards were made with resin content 15 phr, curing pressure 13.72 MPa,
 ....
tH
\iKt ‘Lii1:I
it
¢!~3Pt@r§---___- - __ _ b _ - _ ,_.,,._._._.­

cure temperature 150°C, P: F ratio l:2.9 and CNSL: P ratio I00: 0 and varying cure
times.

| 0 ,-*"~-"-¢'~—~""~"~*"""—“"'-"~'~*—"—'-'-“ '~'—"‘ '--‘“=‘~""-:=‘—‘;7-"—“"-""'*-'-'~'*—"=‘-'-"T¥ ~‘—""'*~-'—‘=*~I-=—‘-'-—-1'--=;—_-=-;—_==-.T_—;i_'.'.-_-“.1.-\-_==~=-;.~__-~».».-~..--.,~.--.@--...~»--~\~--.»-u--W.-~..-N».-¢~_»»-~_--W-»_.~,

8 H l***;~>l"*­

‘* wee. _
00 5 10 15 20_25 30
_
2 ~Rz;~e~=~¢——~——¢;~~———;xe——1——X
i““%“%fiF““““*~1e~—————% ‘
4"-"'*"~ ~-» -A
i

‘.

Cure time (minutes)

-+- Density (Kg/m3) ——-I—— Moisture content (%) —-A-— T.S(para|leI)

-><-- T.S(perpendicular) —-xe—— CompressibiIity(mm)

Fig. 5.8 Variation of properties of the particleboard

(Case l) as a function of cure time

Fig. 5.8 shows the variation in density, moisture content, tensile strength
(parallel), tensile strength (perpendicular) and compressibility with cure time.

Density is almost constant when the cure time varies between 5 and 25
minutes.

Moisture adds to the weight and can also affect the environmental durability
of particleboards. Moisture content is almostconstant when the cure time increases
from 5 to l5 minutes. But there is a slight fall from 15 to 25 minutes. But such long
cure times can lead to degradation of pI'OpCI'liBS.

When the cure time increases tensile strength (parallel) increases up to about
15 minutes. Tensile strength is almost constant with further increase in cure time.
Optimum cure time is about 15 minutes from the viewpoint of tensile strength
(parallel).
 Development of Particleboard

Tensile strength (perpendicular) is found to be maximum when the cure time

is 15 minutes. Above this time degradation of resin or sawdust can occur which
decreases the bonding strength. When the cure time is about 15 minutes the board
shows acceptable values. l 5 minutes are seen to be the optimum cure time.

Comprcssibility decreases when the cure time increases from 5 to 15

minutes. Thereafter there is little change in compressibility. At this point the
particles were in their most compact form. Therefore no further decrease in volume
could take place.

60 - ... .. .. ..
50.

10 € 1
40 1‘

0 5 10 15 20 25 30
Q _ . _......_.....__...._._.-.-__..-.-._...._..-._.-..- ._......_..--_.,,.__....._..-__..-­

Cure time (minutes)

-¢— Water absorption (%) —-I—— MOR(MPa)

Fig. 5.9 Variation of properties of the particleboard

(Case 1) as a function of cure time.

Water absorption decreases when the cure time increases from 5 to 25

minutes.
 i400lj
Chan"-’1§__ i _ _ as _ s ____.,,_,_.­
There is an increase in MOR when the cure time increases from 5 to 15
minutes. Further increase in cure time results in reduction of MOR. A cure time 10

1090
800

200
I
minutes is sufficient to get a board with a standard value of MOR.

600 1 3 l

0 5 10 15 20 25 30
0 s_.__.__..__.__.._.___..,_-_.__.__. __.__.-__.____..__...__.._._____.._.. .._.______.__.____....____.._.__.__,._..__..._.__..__...__1

Fig. 5.10 Variation of MOE of the particleboard

Cure time (minutes)
i

(Case 1) as a function of cure time

Fig. 5.10 shows the variation in MOE with cure time. MOE is maximum at
around 15 minutes.

c. Effect of curing pressure

Particleboards were moulded with cure temperature 150°C. cure time l5
minutes, resin content 15 phr. P: F ratio l:2.9, CNSL: P ratio 100:0 and varying
curing pressures viz. 3.43, 6.86, 10.78 and 13.72 MPa. The boards made at 3.43,
6.86 and l0.78 showed very low bonding strength and the results are not
reproduced here. Hence a maximum pressure of 13.72 MPa is needed.
 Development of Parficleboard

d. Effect of resin content

To study the effect of resin content on the properties of particleboard,

particleboards were moulded with curing pressure 13.72 MPa, cure time l5
minutes, cure temperature 150°C, P: F ratio l:2.9 and CNSL: P ratio 100: 0 and
varying resin contents

.......». -1,........\....~\,-......... ..».\...........--...\, .-..... .....~\.......-..4-............ |IAI\ ...,.........-._.--.~\,. - Mt.-t,.. ...\,...~w .-......--~..~.--..... ,- ..\...,.........

10 M

l {'
2;;it-~I"'f
X’ e
O 5 10 15 20 25 30
;""'-_-'--F_‘

Res in come nt (%)

-4- Density (Kg/m3) ——I—— Moisture content (%)

_-¢- T.S(paral|el) ~—a<-— T.S(perpendicuIar)
-x— Cornpressibility(mm)

Fig. 5.11 Variation of properties of the particleboard

(Case l) as a function of resin content

Fig. 5. ll shows the variation in density, moisture content, tensile strength

(parallel), tensile strength (perpendicular) and compressibility with cure time.

A higher resin content increases the average density of the board. A higher
density leads to a higher strength. But it is undesirable in particleboards because
panels become inconveniently heavy. Although many other properties improve
with density practical difficulties arise because of the inability of nails to pearce
dense particleboards. On the other hand a low density is meaningful only if
mechanical and other properties are satisfactory. There is a small increase in
density as the resin content increases from 5 to 25%. The resin content has to be
§l'“P"-1'5 , _ _ - _ KKKKKKKKKKK - _ _
decided based on changes in properties which are more critical and more sensitive
to resin content.

There is a gradual decrease in moisture content as the resin content increases

from 5 to 25%. The fall in moisture content with increase resin content can be
attributed to many reasons. The higher exothermic temperature reached at higher
resin content can lead to a more effective expulsion of moisture. Further, a more
effective encapsulation/ bonding of the fibers at higher resin content can prevent
subsequent moisture absorption by the particleboard.

There is a gradual increase in tensile strength (parallel) as the resin content

increases. A stronger bonding of the fibers can be expected at higher resin contents.

There is a sudden increase in tensile strength (perpendicular) as the resin

content increases from 5 to 15%. When the resin content is more than l5 % the
board shows tensile strength values as specified by the standards. Below 15% the

. §
resin content is not sufficient to give cohesion between the fibers.

There is hardly any dependence of compressibility on resin content.

50 it K .
it

it

10 if

0 5 10 15 20 25 30
Z

-.__--_-_--_" _---1-_-_.-__\-__--1-._.___..__-.-.1-.1.____.1-§-_-___».1_._-~__\.;-____--._- 7‘-_r.-ah;-._ —_ ~_-- _ -._ _ _ ___ _ _ _

2

Resin content (%)

-0- Water absorption (%) -—I- MOR(MPa)

Fig. 5.12 Variation of properties Of the particleboard

(Case 1) as a function of resin content

Fig. 5.12 shows the variation of water absorption and MOR with resin content..
 Development of Particleboard

Water absorption decreases gradually as the resin content increases from 5 to

25%. Encapsulationf binding of the fiber by the resin and closing ofthe capillaries
within the board as the resin content increases can be the reason for this..

MOR increases gradually as the resin content increases from 5 to 25%.

When the resin content is about 10% the board shows commercially acceptable

iI t:;
values.

3900 V2“

2500 P

O00
500
1000 l

500 ;

O 5 10 15 20 25 30
O lL....i...._...._..,...___i......_.,...__...~._,....__.~__..-.-._......_., ,..__.-.,_,.-__....---__..._._...-_~...._.,..__.\..-__. _.-..__.... ,---...._._....._......_.\..---¢

Resin conte nt (%)

Fig. 5.13 Variation of MOE of the particleboard

(Case 1) as a function of resin content

Fig. 5.13 shows the variation of MOE of the particleboard as a function of

resin content. There is a sudden increase in MOI-Z as the resin content increases
from J5 to 20%. Above 20% MOE is almost constant. Around 20% resin content is
necessary to meet the commercial specifications as far as M OE is concerned.
_______** f — i i —*
Chapter 5

1 9
e‘. Effect of P: F ratio

11i
8 __,_.,-0
‘O 1‘----...~...Q--w-...._\ .-..-v..-.-.4-,.~..--._\-,_.---,.~’».-._--.»-,----..<-u-_--.~--~__~_-..-..~._\.__-~---_~.~_-»..-,.~-..-_»--».~--~_-_~_-.~-~-_»¢--c._»-_---»--w--a.-....._,.._w.. --.-_-.\

'- 6 ~3
4 3‘ _ n____‘-__,<_e _ ee i=4‘
0 >~ eie”
01:00.9 01:01.3 01:01.8 01:02.2 01:02.6 01:03.1
I

P:F ratio

s-+- Density (Kg/m3) —-I-— Moisture content (%) ——A-—— T.S(paralleI)

-><-- T.S(perpendicuIar) -—>x-- C0mpressibility(mm)

Fig. 5.14 Variation of properties of the particleboard

(Case 1) as a function of P: F ratio

Fig. 5.14 shows the variation in density, moisture content, tensile strength
(parallel), tensile strength (perpendicular) and compressibility with P:F ratio.

Density is almost constant when the formaldehyde content changes from

l:l.l to it 2.9.
Moisture content is almost constant when the formaldehyde content increases
from l:l.l to 1: 2.9. The slight increase indicated may be due to greater presence of
CH2OH groups as the formaldehyde proportion increases.

Tensile strength (parallel) increases as formaldehyde content in¢;ea5¢5_

Bonding between the fibers is good when a resin containing higher >mm....... Ar
 _ _ _ _ _ DevelopnferttgofParficleboard
formaldehyde is used. At high formaldehyde content the degree of crosslinking is
high.

ii
Particleboard prepared from resin containing higher amounts of formaldehyde
showed slightly improved bonding strength. Resin with high formaldehyde content
may be more reactive towards fibers apart from being more crosslinkable.

‘Iit.1 5
Compressibility decreases as formaldehyde content increases. A higher
degree of crosslinking and binding between sawdust and resin may be responsible

._ §
for this.

l1aiii
2§1
g1; »—
t

.
4_a ~—0
50 3 .............. M ­

elf ’ k ‘P '
10 Q-=-#"“““" =
r j_ra_fi_._
_._?— I
1

‘» —— _—__—_— — av‘ —_ _—_—_- _-,7-_— — — -.--___.~...____-~....-..,---_i..-.-.~ ~— —_— — __—=,— _ — -—_~~, — __»-_'---i_.,..~-_i._-..-..i._..~---i..-Q“?-a

01:00.9 01201.3 01:01.8 01102.2 01:02.6 01103.1

P:F ratio

—o—- Water absorption (%) ——I-—- MOR(MPa)

Fig. 5.15 Variation of properties of the particleboard

(Case 1) as a function of P: F ratio

There is not much variation in water absorption as the formaldehyde

content changes.

MOR increases gradually as the formaldehyde content increases. Resins with

P: F ratio 1: 1.7 and less shows values higher than that required by the standard.
C_liagte[5_ _ *_ 0 j j 0 i _ i 0

800 0 _
it ks it.
1000 .m_.M-.~._ .~._-...~.-W_,.~w_e.‘._.~.,._-r._»._v._M_oaa; - to 1 <1 o _\'¢"-1%"'\"'--\~v~fln1o\1-‘

400 1
200 J
600 ;

01200.9 01201.3 01101.8 01102.2 01102.6 01103.1

P:F ratio

Fig. 5.16 Variation of MOE of the particleboard

(Case 1) as a function of P: F ratio

Fig. 5.16 shows the variation in MOE with P: F ratio. MOE increases only
slightly as formaldehyde content increases.
 s4!
i _ _ f W _ y_ fDpevelopment0fyPaiftt'cIeboard

f. Effect of CNSL: P ratio

6t i
10 7"
16 W ..-_.t..~.-._~_..-_e~e....c.._.~..t-..-..._ ._ - ... _

8-+§
14 t
12 ,t

2 _E K _*—
****‘*;-i->"*
“:_-F__ _ if
t 7“;i ___
——i—**r*
_ ___
O 25 50 75 100 K _:y_____
hi-P}?_
as _ -4

0 _~:o_ eta.-— _.— -can 1: J -—. _~_~. --~_-.~._~_o~o ~ ~=-_——_--.1-J_;-up

CNSL content (%)

-+— Density (Kg/m3) -1- Moisture content (%) —a-— T.S(paralIel)

--><-— T.S(perpendicuIar) —x-- C0mpressibility(mm)

Fig. 5.17 Variation of properties of the particleboa rd

(Case 1) as a function of CNSL content

Fig. 5.17 shows the variation in density, moisture content, tensile strength
(parallel), tensile strength (perpendicular) and compressibility with CNSL: P ratio.

Density remains almost constant as CNSL content increases.

Moisture content increases initially as CNSL content increases.

Tensile strength (parallel) decreases sharply as CNSL content increases up to

50%. This is due to the lower reactivity of CNSL due to the presence of the long
side chain ot‘CNSL.

As the CNSL content increases bonding strength decreases. CNSL has a

10112 side chain, which induces a plasticizing action that can improve the impact
Cha_pter§ _ _ i _ _

at
properties but decrease the bonding strength compared to phenol. Crude CNSL also
contains constituents that may not react with formaldehyde. IS specifiction for
tensile strength (perpendicular) is a minimum of 0.8 MPa. Even at 50% CNSL
there is a bonding strength of 0.8 MPa for the board. So a particleboard with good
bonding strength can be obtained even afier replacing 50% of phenol by CNSL.

Compressibility is seen to increase drastically with CNSL content. The

it
It i.
ti
presence of the substituted phenol in CNSL leads to less effective binding and
consolidation. Hence compressibility increases with CNSL content. However at
50% CNSL content compressibility is not excessively high.

10 ;
40
*aJ *t—
_ - —~-~+
1 fi* ~ +ffi%__e
‘ it
O 25 50 75 100
0 ; __ To -__. _ _ i _._ u-.. u ....__ c
CNSL content (%)

—o— Water absorption (%) —I— MOR(MPa)

E:

Fig. 5.18 Variation of properties of the particleboard

(Case 1) as a function of CNSL content

MOR decreases as CNSL content increases.

There is slight decrease in water absorption with increase in resin content

beyond 50%. The hydrophobicity of CNSL can be the reason behind this.
 800 @;

600 it

400 a

200
Q0 25
tl=2Il
_ 1 _ c c : ; : : i o ; A 1 _ _ : 1 _ _ _ t _D¢v5={vr3w¢"3 Pffiflffiviclzeerfi

r ———~e ~ 11-e._ ,
‘ ........... t---\--_~.-.-----_~~ .~.~-........~»- ---.~----_~.~_.~,_~,.-av‘-_~ ~\- -.~\\--».-__h-,-\-.._--.-.¢-»-.\---.¢¢~- . .__..\.-.--_..w-- .- Q.» .- . .-W ..w.-.--_.,

\t

tI

c _ 50_ 75
\

_ 100
__
.'
5

CNSL content (%)

Fig. 5.19 Variation of MOE of the particleboard

(Case I) as a function of CNSL content

MOP. decreases as CNSL content increases. At 50% CNSL there is only a

small change in MOE. Hence half of phenol can be effectively replaced by CNSL.
Chapter 5

5.5.2 Effect of moulding conditions and stoichiometry on the properties of

particleboards from dry moulding powder consisting of CNSl-phenol- hexa
copolymer (Case 2)
a. Effect of resin content

14~

I.
I_

. .—1*"U\.‘ ‘ ­
0 51.1.
10 :4.//~*~<t__:
15 20 25 30.
'M n up Resin content (%)
-0- Density (Kg/m3) -1- Moisture content (%) —a— T.S(paralle|)
—><— T.S(perpendicular) —x—- Compressibility(mm)

Fig. 5.20 Variation of properties of the particleboard

(Case 2) as a function of resin content

Fig. 5.20 shows the variation of density, moisture content, tensile strength
(parallel), tensile strength (perpendicular) and compressibility with resin content.
Density is almost constant when resin content varies from 5-25%.
There is a drastic fall in moisture content when the resin content varies from
10- 15%. In the higher range of resin content, 15-25%, it is almost constant.

There is an increase in tensile strength (parallel) as the resin content

increases from 5 to 25%. As the resin content increases bonding between the filler
particles becomes stronger and hence tensile strength increases. The values are
maximum at about 25%.

Tensile strength (perpendicular) increases steadily as the resin content

increases. When the resin content is about 10 phr particleboard shows tensile

2l6
 Development of fqrticleboard

strength values greater than 0.8 MPa specified by the IS 2380 (1977). It can be
inferred that beyond 10% resin content a cohesive composite structure is
established. At this stage a continuous bond cementing individual fibers together
appears to have developed. The percentage binder required is less in this case
compared to Casel.

Compressibility decreases slightly as the resin content increases. As the

bonding between the filler particles increases the free space available decreases and

1F .­1
hence compressibility decreases.

*0 .~.-..¢...-----~-_-_....-_-~ -w .- QC MR ....,.....\-....,,.-M.-...-.1.“-.-..w-..,..-.,-...... ­

40 t

10 ll _._ ~-._~_,* __._.

ll

0 5 10 15 20 25 30
$..,._.._..._.._..._...,_..s_....__..._.._..._~._..._.._..._,~__...._..-._..._..-,_.._.._...-_.._..__...__..._, ._.,_..-_.,.._. .._..~_>

Resin content (%)

-o- Water absorption (%) e-n-- MOR(MPa)

Fig. 5.21 Variation of properties of the particleboard

(Case 2) as a function of resin content

Fig. 5.2] shows the variation in water absorption and MOR with resin
content.

There is a sudden increase in MOR when the resin content increases from l0
to 15 phr. When the resin content is more than l0 phr particleboard shows values
greater than the minimum value l 1 MPa specified by the standard. This behaviour
is similar to the case of tensile strength (perpendicular). Both graphs suggest a
sudden improvement in the performance of the board beyond l0% resin content.
However MOR values given in the specification is reached at as low a resin content
Chapter5* i j i j _ 4 i
as 10%. Hence the board shows a superior MOR compared to conventional
samples.

There is a sudden decrease in water absorption when the resin content

increases from 10 tol5%. As the resin content increases there is better bonding
between wood fibers. This provides less pathways for water to penetrate the
composite material. It is possible that at l5% resin content, there is effective
encapsulation of the fibers and closing of the capillaries.

4000 ¢

1000 "
iE
000 31

000 é
1

1.
1 _. !4_ —y s 1-4
l

0 5 10 15 20 25 30
Resin content (%)

Fig. 5.22 Variation of MOE of the particleboard

l

(Case 2) as a function of resin content

There is gradual increase in MOE as the resin content increases up to 15 phr.

Above 15 phr resin content MOE is almost constant.
 _ _ _ U Qweiopiizeiir of Particieboard

6.
b. Effect of P: F ratio

10 Ti /
I 2 .-ya.-...w.,i.“..,.~,..-.._..~..,--_ ....-wt. .,..._._,~v.w-..........,.v-.»-_._ M -~ _-.,,.,..~-- ...»~v.\,..v_..~_»A~.,v.. ..v..,...... ._._¢\~w,.~,- ..“~~-V

8y k_#_¥_, +*
42 =1
1 es:
~-~~ e
0% s fie: 3:~~­I
01:00.9 01:01.3 01:01.8 01:02.2 01:02.6 01:03.1

-0- Density (Kg/m3) —|— Moisture content (%) -;- T.S(paraIleI)

P:Fratio

-+<— T.S(perpendicular) -—~>x— Compressibitity(mm)

Fig. 5.23 Variation of properties of the particleboard

(Case 2) as a function of P: F ratio

Fig. 5.23 shows the variation in density, moisture content, tensile strength
(parallel), tensile strength (perpendicular) and compressibility with P: F ratio.

There is some decrease in density as the formaldehyde content increases.

There is greater reduction in weight as the formaldehyde content increases due to
elimination of more molecules of water of condensation.

Moisture content decreases slightly as the formaldehyde content increases.

There is a gradual increase in tensile strength (parallel) as the formaldehyde

content increases. A more crosslinked and compact structure of the resin may be
responsible for this. A higher formaldehyde content may lead to more effective
interaction with wood fibers because of higher methylol content.
¢!*“Pf@*5_ on 0 _

E
A greater tensile strength (perpendicular) is observed as the formaldehyde
content goes up. This is in agreement with the observations made earlier. At higher
formaldehyde content the resin has higher adhesive strength and cements the wood
fibers more effectively. Higher formaldehyde content leads to a higher content of
methylol groups and a greater degree of crosslinking.

Compressibility decreases as the formaldehyde increased up to about 1:2.3.

There are fewer number of voids in the composite material as the formaldehyde

1 i,
content goes up.

40l :4‘_ E;
50 _ _ - ;
U w — ~~ » we­

i__~a~
i ___:__ __.
10‘ I­
01:00.9 01:01.3 01:01.8 01:02.2 01:02.6 01:03.1
P:F ratio

-4- Water absorption (%) ——I— MOR(MPa)

Fig. 5.24 Variation of properties of the particleboard

(Case 2) as a function of P: F ratio

Fig. 5.24 shows the variation in water absorption and MOR with P:F ratio.

There is no variation in water absorption as the formaldehyde content

changes.

There is a steady increase in MOR as the formaldehyde content increases.

The MOR values satisfying the Indian Standards is reached at a P: F ratio of about
l:l.7.
 1
l‘ 1
2
E
0 a,__,__::,,;,,___::::__:c_: _ J?@P€'QPI'?§"£K°)f*I“!"?P'€bP¢?'4

4000
5000 0 _
O00 ;'

1000 1;
11

l1

0 c_.______. 0,, ,0 0, ____c ,0 0 ._-_;.a.._..,.a_;.ae;~i_0, 5 _.a._.._.._.__.._

01:00.9 01:01.3 01:01.8 01:02.2 01:02.6 01:03.1
P:Fratio

Fig. 5.25 Variation of MOE of the particleboard

(Case 2) as a function of P: F ratio

Fig. 5.25 shows the variation in MOE with P: F ratio. MOE increases as
the formaldehyde content increases. At the lowermost formaldehyde content
studied namely l:l.l molecules of the condensate tends to be large. At such low
formaldehyde content, methylol groups are fewer. On crosslinking a less stiff
network structure is established because of lower methylol functionality. But -at
high formaldehyde content (> l:2.3) a high functionality leads to a highly
crosslinked network.
C liapter 5

14
12;
.3 il
“
c. Effect of CNSL: P ratio

86‘)
1 ‘..
10 ‘i lt
‘ 6 . ........................... ._....,<~.-.~w“». ....... ._ ........... ---..\.--».~ .... .-wv-.~-\\-.\-0....-._. ......... ..,,_,,,__. ___________ _,__~_~,_____ _______ __,_,,__.,____________ ___ ,____ _

30 Lei? i" s ;_
20 40 60 80 1003
_¢- Density (Kg/m3) —|- Moisture content (%) _;- T.S(paraIlel)
CNSL content (%)
l1

—a<-— T.S(perpendicular) -ax—- Compressibility(mm)

Fig. 5.26 Variation of properties of the particleboard

(Case 2) as a function of CNSL: P ratio

Fig. 5.26 shows the variation in density, moisture content, tensile strength
(parallel), tensile strength (perpendicular) and compressibility with CNSL: P ratio.

There is only a very small change in density as the CNSL content increases.
Side chain of cardanol or other phenolic compounds in CNSL can lead to loose
packing of the chain. The adhesive properties tend to be poorer in this case. Hence
a fall in density can be expected.

Moisture content decreases as CNSL content increases. A higher percentage

of CNSL leads to a higher percentages of aliphatic compounds in the form of side
chain of the CNSL molecule. CNSL is more hydrophobic than phenol.

Tensile strength (parallel) decreases gradually as CNSL content increases.

Particleboard based on pure CNSL- fomialdehyde copolymer is about half as
strong as that based on pure phen0l- formaldehyde copolymer. The lower reactivity
of C NSL, steric hindrance caused by side chain etc. can lead to a polymer of lower
strength and binding Dower.
 ._
ff _ L __ __ i _ i _ _ _ g _ Deveflogmentg0fPa§ticleb0f1rdg

The perpendicular tensile strength or bonding strength of the resin is not

seriously affected on addition of upto 20% of CNSL. Beyond 20% the strength falls
drastically. Tensile strength (perpendicular) is higher than the value specified by
Indian Standards when the CNSL content is less than about 50%. Consideri.ng the
low cost of CNSL and its renewable nature use of CNSL can be a worthwhile
proposition.

Compressibility increases marginally with CNSL content.

,i e ‘jg!
_..-.~».~--..---, - _. wu ~.._.-~,»--- w- - N -~»- w vv

&' ,7 ___~-** i7__'f 7 V

—+ 1 a '
0 25 50 75 100
7"_;:_ ;'_ :_— ' '__~.-in-map ' ~: ~ ;'— ' ;1 ~;_—_r -_~._-_-_ _"_:' _>-_-_ ' —__—' ' ;_— _ ~ i—i;-_--_-_—_— if ———<_— —;—_ 7 7 "'_'_'_'é

CNSL content (%)

-0- MOR(MPa) —a-- Water absorption (%)

Fig. 5.27 Variation of properties of the particleboard

(Case 2) as a function of CNSL: P ratio

Fig. 5.27 shows the variation in water absorption and MOR with CNSL: P
ratio.

There is not much change in water absorption as CNSL content changes. The
slightly higher water absorption indicated at higher CNSL contents may be caused
by slower and possibly incomplete reaction between hexa and C NSL.

There is a small decrease in MOR as CNSL content increases. CNSL gives

some flexibility to the resin.
_(_I'hapter

4000
’~
000
1000
000 =
5 2l
0'
‘
§
é
5
i
§
O 25 50 75 100 CNSL conte nt (%)

Fig. 5.28 Variation of MOE of the particleboard

2
i

(Case 2) as a function of CNSL: P ratio

Fig. 5.28 shows the variation in MOE with CNSL: P ratio. MOE shows a
slight fall on addition of more and more CNSL. Here also the lower modulus may
be the result of a more flexible resin resulting from the presence of CNSL.

5.5.3 Effect of fillers

Table 5.3 shows comparison of properties of particleboards made from

CNSL —phenol- hexa resin using different fillers (resin content — l5 phr, cure time
15 minutes, cure pressure 13."/2MPa, cure temperature 150°C, CNSL/P — 50/50, P:
F l:2.9). Board made from rice husk has comparable values of tensile strength
(perpendicular). Rice husk leads to a board of much lower density than that made
from sawdust. Rice husk board has a much lower tensile strength (parallel) while
tensile strength (perpendicular) is only marginally less. MOE and MOR are both
very low compared to sawdust board.
_ _ _ _ _ _ _ _ : : : : i ; : __ __ _ _ _ _ _ _ _ _ _ 6_D?'{"{"F3"!‘3i't_°[Iiaftfcieliofirq

\l
Table 5.3
Comparison of properties of particleboards made from CNSL ~phenol- hexa
resin using different fillers (resin content — 15 phr, cure time 15 minutes, cure
pressure l3.72MPa, cure temperature 150°C, PIF - 50/50)
II

I T? 5 T 5 IiMOi;t;;e: lwmer "l"en*silefiI 5 Lleintsilei T I I I ; J I 1 5 II

I Density’; I IStren;;thI Strength I MOR n MOE (Compres­ II

IIs6.w6ustI
I sII
II

I Finer 1‘‘gm/cc
Content abSOrpti0nParallel InIPerpendicularI(MPa)I(MPa)I sibility
I__l_,J__,_,,,_,,_ ____, _ .. ,,_I ,__*
I

I _______ I 6 _I7(l\T/l'?ai)__II:s~(!Y,[l__)al__;II._ II

II ___.23___ *' I 1.2 I 36.9 H4156 L 0.98

10 A 10.8
_ _ m __ , — Z 77 7 4 ’ ’ 7 7’ _—y-,7" 7’ L,’ I-j 4- ; 2- 1 1
I

Rm ‘ . II16.4
.92 I 695 1. 3.066
II

I(___l19S§(_)___*____%_%*__
243, 8.88 _ _ _ _ _ _ i l I 7_ t__)_§____sL__6__L
t 7 7 7 _ _ _ _ _ __ i : f Z ii-if I‘
_— _% 7— I

Table 5.4 shows comparison of properties of particleboards made from

CNSL —phenol- hexa resin and CNSL-hexa resin (resin content — 15 phr, cure time
15 minutes, cure pressure l3.72MPa, cure temperature 1500C, CNSL/P — 50/50, P:
F l:2.9). Particleboard moulded from CNSL-phenol-hexa resin shows lower
moisture content, water absorption and compressibility and higher tensile strength
(parallel), tensile strength (perpendicular), MOR and MOE compared to
particleboard moulded using CNSL~hexa resin.
 §_'ha_ptef5_*___ __* if pg

ur , Table 5.4
Comparison of properties of particleboards made from CNSL —phenol- hexa
resin and CNSL-hexa resin (resin content — I5 phr, cure time 15 minutes, cure
press e 13.72MPa, cure temperature 150°C P/F — 50/50)
7 5 5* 5 "5 5 5 ‘15 55 5 TV 5 T T : .: 5:‘ 5 H 5; 55 5"; : 5 T5 *5 '5 *5 —
~ . 4‘Moisturei
Tensile
Water 1 l Tensile W 1 1‘ 1
R _. Densityc t t1‘b ti Strength Strength MORMOE1Compres­
85'“ 1 m/‘ . °“ 6“(0/0)
g (.C1 6* 5°’? °“ Pa 111
1 (0/O)
- - - - - - .l~.(MP.a)“ -<MP==1-- gT3 Perpendicular(MPa)i(MPa)
C sibility
1

1W111111
1 CNSH)"
CNSL-hexa
116' it '32
hexa Q1:
J1 1‘1.111
14101‘ L108L1:
i1 _8 _1 40_ ‘A
1 16
u. 4_ 0.8
' 13694156
' 1 ' 1 11.803
_ _118.92
Hi 1 774
‘, , 1.983
i

5.6 CONCLUSIONS

The mould design and the moulding procedure adopted for particleboard
moulding by both the methods (Case l and Case 2) are found to be effective. This
can be a starting point for a moulding process to make larger mouldings.

The cure temperatures studied (I50, I60, 170, 180 and 190°C) are found to
affect the properties of the board only marginally. The overall picture favors a cure
temperature of l500C. Most properties are optimal at about 15 minutes cure time.
The resin content affects the tensile strength (perpendicular) drastically. It shows
acceptable values at any resin content beyond 15% when a binder consisting of a
reactive mixture of CNSL and hexa is used. A P: F ratio of l: 2.9 is required to give
sufficiently high values of bonding strength. There is a slow but steady increase in
tensile strength (perpendicular) as the formaldehyde content increases. The presence
of CNSL lowers the tensile strength values. But about 50% CNSL can be used to
replace phenol to give a board with acceptably high values of bonding strength. ln
general, CNSL content increases the compressibility of the board.
A resin content of 10% gives sufficiently high values of bonding strength
and acceptable values of water absorption when the powdered resin resulting from
 _ Development of Partieleboard

the condensation of CNSL, phenol and liexa is used. Both MOR and MOE reach a
plateau at 15% resin content. The P: F ratio has very little effect on the bonding
strength which is uniformly high. Increasing CNSL content leads to a board of
lower tensile strength but the bonding strength is still high upto 50% CNSL content
in a mixture of CNSL and phenol used for the binder.
Chapter, 5

REFERENCES
H. Kubler, Wood as a building and hobby material, Wiley and Sons, lnc.,
Canada (1977).
A.Knop, W.Scheib, Chemistry and Application of Phenolic resins, Springer­
Verlag, New York (1979).
R. Viswanathan, L.Gothandapani, Bioresource Technology, 67(1), 93-95
(1999)
A. Sampathrajan, N.C.Vijayaraghavan, K.R.Swaminathan, Bioresource
Technology, 35 (1), 67-71 (1999).
A. Sampathrajan, N.C.. Vijayaraghavan, K.R.Swaminathan, Bioresource
Technology, 40 (3), 249-251 (1992).
P. Khristova, S.Gabir, Bioresource Technology, 58 (3), 319-321 (1996).
E.G. Jan, J .A. Martin and R.P.Edwin, Indusrial crops and products, 20 (1), 97­
l0l(2004)
A.N. Papadopoulos, C.A.S Hill, A. Gkaraveli, G.A Ntalos, European Journal
of wood and wood products (2004)
A.N. Papadopoulos, .l.B. Hague, lnd. Crops and Products, 17(2), 143-147
(2003)
TS: 840 (1964)
K.V- Sarkanen, C-W. Ludweg,, Lignins, Wiley- lntersciences, New York
(1971)
W. Alfred, Wood and Fiber Science, 23(1), 69-74 (1991)
H.T.Wegner, United States Department of Agriculture, in Encyclopedia of
Polymer Science and Engineering, Vol 17, A Wiley lnterscience Publication,
U.S.A (1985).
B. English, J.A. Youngquist and A.M. Krzysik, Lingnocellulosic Composites,
1n: R.D. Gilbert Ed. Cellulosic Polymers, Blends and Composites, New York,
Hanser Publishers, 1 I5-130, 1994, Ch. 6
Chapter 6
CONCLUSIONS

The important conclusions from the study are the following

L CNSL, phenol and formaldehyde can be eo-condensed to get a CNSL-

phenol- formaldehyde resole resin with a typical Mil ~835 and l'Yfw = 3345.
Melting point is in the range of 70 to 80°C and a typical decomposition
temperature is 500°C.

2. Of the two methods for preparation of resin investigated, the method

involving a condensation step followed by air-drying for 4 days IS more
acceptable because it gives a shorter cure time subsequently

3. Useful adhesive systems based on neoprene and CNSL -phenol-hexa

copolymer can be formulated. Such adhesives are more suitable for AI- Al
bonding rather than HR-AI or HR-HR bonding.

4. Cure time of 2.5 hours and a cure temperature 140"C are found to give the
best results for these adhesives.

5. The resin used for adhesive formulation is found to give the best
performance at 45 to 55 phr of the resin and a total phenol: formaldehyde
ratio of 1:2.9. Total solid content of the formulation is optimum at 38 %

6. A coupling agent 3- aminopropyl triethoxy silane is found to improve the

performance of AI- Al adhesive bonds.

7. The best results are obtained for the resin resulting from condensation of
pure phenol with formaldehyde. However inclusion of upto 25% CNSL
gives an almost equivalent performance.

8. The copolymer obtained by condensation of CNSL and phenol with hexa

when added at the rate of 15 phr improves the ageing characteristics ofNBR,
SBR and HR with respect to retention in tensile strength, modulus, tear
strength and elongation at break. All these rubbers behave in a similar
fashion in this respect.
Chapter 6

Vulcanizates containing resin with P: F ratio 1: 2.9 shows the least change in
properties on ageing.

Although resin based on pure phenol gives the greatest improvement in

ageing characteristics of NBR, addition of CNSL upto 25% still resulted in
substantial improvement.

Based on studies of SBR, CNSL by itself at 15 phr has the ability to improve
the ageing characteristics.

Ageing studies on EPDM and NR show no positive effect on addition of

CNSL- phenol- hexa resin. In the case of CR which has inherent resistance
to ageing no effect is noticeable.

The mould design and moulding procedure adopted for particleboard

moulding are found to be effective. This can be a starting point for a
moulding process to make larger mouldings.

When a binder consisting of a reactive mixture of CNSL and hexa is

employed a minimum resin content of l5% is needed for optimum
performance of particleboard.

For particleboard based on rosewood sawdust and CNSL based resin, the
optimum cure temperature is 150°C and cure time, l5 minutes.

When a reactive mixture of CNSL and hexa is used as the binder a high
formaldehyde content (P: F ratio l:2.9) is needed. But when the powdered
resin is used as the binder even low formaldehyde content typically l:l.l gives
adequate bonding strength. In both cases replacement of phenol to the extent
of 50% by CNSL gives an equivalent performance by the particleboard.

When a powdered resin resulting from the condensation of CNSL, phenol

and hexa is used as binder 10% resin concentration gives the accepted values
of bonding strength for the board.

The study amply demonstrates the utility of CNSL for three important
applications in polymer processing.
Listvf abbreviations andsvmbols D 1
ANSI Ur
American National Standards Institute

ASTM —
American Society for Testing and Materials
CNSL 0­
Cashew nut shell liquid

vp —
Centipoise
CR Q
Chloroprene rubber
DBP -A
Di butyl phthalate
DCPD ­
Dicyclopcntadiene
DIN —
Deutsches lnstitut fur Normung
DOP _
Di octyl phthalate
DSC on
Differential scanning calorimetry
ENB 1
Ethylidiene norbornene
EPDM Q
Ethylene propylene diene monomer
EVA up
Ethyl vinyl acetate
F -n
Formaldehyde
orc —
Gas Liquid Chromatography
GPC w_
Gel Penneation Chromatography
HAF Q
High abrasion furnace black
HCHO ­ Formaldehyde
HMTA ­
H cxamcthylenetetramine
HPLC ¢
High Permeation Liquid Chromatography
HZSO4 1
Sulphuric acid
A bbrev ia tion

IS Indian Standards

IIR Isobutylene~isoprene rubber

KMnO4 Potassium permanganate

MBTS Mercaptobenzothiazol disulphide
min Minutes

mm millimetre

MF Melamine formaldehyde

M g0 Magnesium oxide
MPa Mega pascals
MT Metric ton

Mn Number average molecular weight

MW Weight average molecular weight
Mv Viscosity average molecular weight
ML (1+-4) 100°C ­ Mooney viscosity number. L indicates the large
rotor, 1 is the time in minutes that the specimen is
preheated, 4 is the time in minutes after starting the
motor at which the reading is taken, and 1000C is the
temperature of the test.
MOE Modulus of elasticity
MOR Modulus of rupture
MPa Mega pascls
N Newton

NaOH Sodium hydroxide

NBR ­
pPa ­­
Acrylonitrile- butadiene rubber
NR — Natural rubber

Phenol

PF ­
Phr ­
Paseals

Phenol formaldehyde
Per hundred rubber

PTSA ­ Paratoluenesulphonic acid»

PVC ­ Polyvinyl chloride
PVA<; ­ Poly(vinyl acetate)
SBR ­ Styrene- butadiene rubber
SO;Cl2 — Sulfonyl dichloride
TLC ­ Thin Layer Chromatography
TGA ­ Thermogravimetric analysis
TMTD ­ Tetramethylthiuram disulphide
UF i ­ Urea formaldehyde
UTM ­ Universal Testing Machine
UV — Ultraviolet

WI ­ Weight
ZnO ~ Zinc oxide
List of Publications
“Cashew Nut Shell Liquid- a versatile monomer for polymer
synthesis” Designed Monomers and Polymers, C. Mary Lubi and Eby
Thomas Thachil, Vol 3, No 2, I23-153 (2000)

“Modification of NBR by addition of Phenol- CNSL- Formaldehyde

copolymer” Journal of Elastomers and Plastics, C. Mary Lubi and
Eby Thomas Thachi], Vol 33, No 2, 12]-136 (2001)

“Copolymerization of CNSL and phenol by condensation with

hexamine “ International Journal ofPoly/neric Materials, Mary Lubi
C. and Eby Thomas Thachil, Vol 52, No 9, 793-807 (2003)

“Effect of Phenol- CNSL- Fonnaldehyde on Themial Ageing of

NBR” Progress in Rubber, Plastics and Recycling T eclinology, Mary
Lubi C. and Eby Thomas Thachil, Vol 21, No 3, 201-218 (2005).

“Studies on metal-to-metal adhesives based on CNSL resin” Polymer

Plastic Technology and Engineering , Vol 45, l-6 (2006)

“Effect of Phenol- CNSL- Formaldehyde on Thermal Ageing of SBR"

International Journal of Polymeric Materials (Accepted)

“Paiticleboard from Cashew Nut Shell Liquid (CNSL)” Polymer and

Polymer Composites (Accepted).

“Effect of Phenol- CNSL- Formaldehyde on Thermal Ageing of

Elastomers” International Journal of Polymeric Materials

(Accepted)

“Effect of Phenol- CNSL- Fomialdehyde on Thermal Ageing Of

Elastomers” Journal ofElastomers and Plastics (Communicated)
 0. “Particleboard from Cashew Nut Shell Liquid (CNSL)” Polymer
Plastic Technology and Engineering (Accepted)
11 “Modification of Unsaturated Polyester Resin using Elastomers,”
Journal of Elastomers and Plastics, C. Mary Lubi, K.Ravi, Abdeen
Ahammed and Eby Thomas Thachil, Vol 32, 60-72 (2000).
2 “Synthesis of Unsaturated Polyester Resin- effect of anhydride ratio”,
Designed Monomers and Polymers, C.Mary Lubi, Abdeen Ahammed,
M. Zafeer, and Eby Thomas Thachi], Vol 4, Issue 3, 260-267 (2001)

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