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INTRODUCTION
1
1.1 INTRODUCTION
(I)
The epoxy resins has a wide variety of applications including conventional house-hold
house
systems as binders for floor coatings. Typical applications are :
But the conventionally available epoxy resins don’t meet the expectations requisite in the
field of advanced materials such as flexibility, flammability resistance etc.
The oxirane ring in epoxy is capable of reacting with a variety of chemical agents. On
curing the epoxy rsins become rigid the
thermosets.
rmosets. Variety of chemical compounds such as
2
diluents, coated fillers, ground fillers, curing agent accelerator are added to improve the
resin system properties. The main factors which decide the cure process are
When the chemical structure of the cured epoxy system contains heterocyclic or aromatic
rings or both, its thermal resistivity is higher than a system with flexible chains6. Also, if
the curing agent’s chemical composition contains carboxylic anhydride, imide11, or
hydroxyl-terminated imides12, 13 & imide-acid14-16, the thermal resistance is improved .
Although epoxy resin curing has been extensively researched by different curing agents
of variating structures, however, few reports are available on the application of imide
amines, anhydrides, & benzoxazines. Further no report is available on the use of these
hardeners in carrying out curing in DGBT, (N,N'-
diglycidylbenzophenontetracarboxydiimide), a type of epoxy resin. Therefore, it is of
interest to investigate systematically the effect of the structure of curing agents on the
curing & thermal behaviour of DGBT.
Epoxy Resins wer first synthesized by Dr. Pierre Castan of Switzerl& & Dr. S.O.
Greenlee of the United States in 1936. This technology was sold off to many major
players like Ciba, Huntsman, Momentive Specialty Chemicals etc to name a few.
Epoxy resins are essentially thermosets because after cure they don’t flow on heating
because of permanent locking of molecular chains.
3
The curing of epoxy resins is carried out by addition of hardener. Most common hardeners
are amine based. Typical resin to hardener ratio is 2: 1 or 1:1.
Thus, based on the reactivity of curing agents & the curing conditions, cured epoxy resins
show versatile property, including excellent heat & chemical resistance, high strength,
good impact resistance, high hardness & electrical insulation17,18
The liquid epoxy resins are of low molecular weight & are characterized by a repeating
(Scheme 1.1) structures having secondary hydroxyl group. The degree of polymerization,
is ranging from 0 to 0.5 & two terminal epoxy groups.
A liquid epoxy resin is produced by gradually feeding an aqueous solution of alkali metal
hydroxide into a solution of bisphenol-A in epichlorohydrin, while maintaining the
reaction medium at boiling point, distilling off water in the form of an azeotrope with
epichlorohydrin & recycling the latter, & maintaining a water content of from 0.1 to 0.7
wt.% & a pH value between 7 & 9 in said reaction medium. The liquid epoxy resins thus
obtained have low values of epoxy equivalent & chlorine content (, here n is nearly zero
(0.2)).
CH2-CHCH2Cl HO OH
O bisphenol A
epichlorohydrin
(large excess) NaOH
4
1.3.2 Solid DGEBA Resins
This class of epoxy resin also contains a repeating unit (Scheme 1.1) having a secondary
hydroxyl group. The degree of polymerization is ranging from 0 to 0.5 with two terminal
epoxy groups (II).
O CH3 OH n CH3 O
(II)
Phenoxy resins contain no epoxy groups & are of higher molecular weights, & also true
thermoplastics. They are prepared by reacting epichlorohydrin with bisphenol A &
caustic soda in dimethyl sulfoxide. However, the presence of many free hydroxyl groups
permits cross-linking with various curing agents like anhydrides, triazines, isocyanates &
melamine. The phenoxy resins are also classified as poly (hydroxy ethers) (III):
O O CH2CHCH3
n
OH
(III)
These resins are compatible with many polymers, & are efficient flexibilizers & have also
shown utility in compatibilizing blends of diverse plastic materials. Phenoxy Resin has a
solubility parameter of 10.68, implying excellent compatibility with polar plastic
materials such as Nylon, PU etc. but is incompatible with acrylics, olefins, & vinyls..
5
They have excellent vapor barrier properties (water vapor, oxygen, carbon dioxide) & is
compliant with 21CFR175.300 for indirect & direct food/beverage container coatings, as
well as other regulations pertinent to adhesives in multilayer packaging & plastic
components for containers. Certain grades of Phenoxy (PKHW-series) resins made by
grafting onto the aliphatic carbon segments allow formulators significant advantage in
designing VOC compliant coatings & adhesives.
They have been developed to meet customized requirements like, Chlorinated &
brominated epoxies were used for significant flame retardency properties. The best
combination of cost & performance is obtained with brominated epoxy resins.
Halogenated Epoxy resins are listed as below:
Br Br
H2CHCH2C O O CH2CHCH2
HO OH
Br Br
(IV)
Cl Cl
H2CHCH2C O O CH2CHCH2
HO OH
Cl Cl
6
(V)
O CF3 O
O O
O C C O
CF3
(VI)
The esterification of epoxy resins with commercially available fatty acids is a very useful
process employed by industries for air-dried, protective & decorative coatings. Scheme
1.2
7
O O
CH--CH2 R C OH CH--CH2 O C R
O OH
O
-H2O
CH--CH2 O O R C OH
OH
CH--CH2 O O
O C R
O
Scheme 1.2
Various fatty acid modifiers, include linseed oil, dehydrogenated castor oil, tall in fatty
acid, etc. The chemical resistance of the epoxy esters is generally lower than unmodified
epoxy resins.
In recent years, to improve the toughness, the modification of epoxy resins by amine or
carboxy terminated liquid poly (butadiene-co-acrylonitrile) has also been investigated 19.
8
O OH
O
C OH C O CH2CHCH2Cl
NaOH
O 2 CH2CHCH2Cl O
C OH O C O CH2CHCH2Cl
hexahydrophthalic acid OH
O O
C O CH2CHCH2
O
C O CH2CHCH2
O
Scheme 1.3
O O O
O O
CH2-CH-CH2-O-C-R'-N N-R'-C-O-CH2-CH-CH2
O O
O O
(R'= AMINO ACID GROUPS)
(VII)
21-22
Saito et al synthesized heat resistant aromatic imide epoxy esters (VIII) using
trimellitic acid anhydride & 3, 3’- diaminodiphenyl sulfone.
O O
O
O
CH2-CH-CH2-O-C
C O-CH2 CH-CH2
N SO2 N
O O
O O
(VIII)
Epoxy-terminated imide resins were synthesized by reacting methyl-trimellitimide with
aliphatic diols which on reaction with epichlorohydrin gave N, N’- diglycidyl imide
derivatives (IX).
9
O
O O
O
CH2-CH-CH2-O-C
C O-CH2 CH-CH2
N R' N
O
O
O O
O2
where R'= S
(IX)
CH2-CH-CH2-N N-CH2-CH-CH2
O
O
O O
(X)
Laminates moulded from these novel resins demonstrated flexural strength retention at
260oC in the order of 70% based on short-term exposure.
10
O O
O
COCH2 COCH2
CH3COOH O O
3'-cyclohexenylmethyl 3',4'-epoxycyclohexenylmethyl
3-cyclohexenecarboxylate 3,4-cyclohexenecarboxylate
Scheme 1.4
O O
(XI)
O
O
(XII)
O O O
(XIII)
The secondary reaction viz., acid-catalysed opening of the epoxide groups, is minimized
at low temperatures & strongly depends on the chemical constituents & the reaction
media.
11
The multifunctionality of these resins provides higher cross-linking density, leading to
improved thermal & chemical resistance properties over bisphenol-A epoxies.
(A) Epoxy Novlac resin / Epoxy Cresol Novolac Resin
Two resins which have attained commercial significance in industry is epoxy phenol
novalac resins (EPN) (XIV) & epoxy cresol novalac resins (ECN) (XV) 30-36. EPN is
synthesized from the phenol-formaldehyde condensates (novalacs) obtained from acid
catalysed resinification of phenol/ or cresol & formaldehyde37,38 by the process of
glycidylation which produces r&om para & ortho-methylene bridges (Scheme 1.5).
HO
R H+
(n + 2) (n + 1) CH2O
O
OH OH OH
R R R CH2CHCH2Cl
CH2 CH2 (n + 1) H2O
n
O O O
Scheme 1.5
39
The functionality of resins increases if the molecular weight of novalac increases .
Branching can be prevented by epoxidation with an excess of epichlorohydrin thus
minimizing the reaction of phenolic OH with glycidylated phenol groups40. The high
functionality of phenol novalac resins (compared to st&ard DGEB-A based resins) results
in increased cross-link density & improved chemical & thermal resistance.
A polyfunctional resin based on phenol & glyoxal forms the basis of a speciality epoxy
resin41-45 (Scheme 1.6).
12
OH
HO CH OH CH2 CHCH2Cl
O O
O
4 HC CH
HO CH OH
tetrakis(4-hydroxyphenyl)ethane
O
O
O O
Scheme 1.6
Very few multifunctional epoxy resins with an aromatic amine backbone, have
commercial significance46-49. Under carefully controlled conditions, they are synthesized
by Glycidylation of p-aminophenol or 4, 4’-diaminodiphenyl methane with a large excess
of epichlorohydrin. This is because such multifunctional resins exhibits limited thermal
stability & polymerizes vigorously under the influence of a tertiary amine50. The structure
of the resins based on p-aminophenol &/or 4, 4’-diaminodiphenyl methane is shown
below (XVI & XVII) & they are available commercially.
O
O CH2CHCH2
O O
CH2CHCH2 N CH2CHCH2
(XVI)
13
O
O
O
N N O
C
H2
(XVII)
14
The following epoxy products when formulated with appropriate reactants can provide
certain outdoor weatherability:
(a) Hydrogenated DGEBA
(b) Heterocyclic Glycidyl Imides & Amides
Curing Agents or Hardeners on reaction with epoxy resin monomers forms epoxy
products66-68. There are several categories of curing agents & are usually liquids.
Examples include:
o Anhydrides such as phthalic anhydride & nadic methyl anhydride (NMA);
o Aliphatic amines such as triethylenetetramine (TETA) & diethylenetriamine
(DETA);
o Aromatic amines, including diaminodiphenyl sulfone (DDS) & dimethylaniline
(DMA);
o Amine/phenol formaldehydes such as urea formaldehyde &
melamineformaldehyde;
o Catalytic curing agents such as tertiary amines & boron trifluoride complexes.
Curing agent selection plays an vital role in determining the final cured epoxy properties
such as pot life, dry time, penetration & wettability etc. Universally, Amine based curing
agents are considered more chemically resistant & durable than based on amide but they
have a tendency to blush in humid conditions. Most of the free amines are carcinogenic in
nature. Whereas amides are more surfaces tolerant & less troubled by moisture69.
15
A description of various amines, anhydrides, & catalytic curing agents is tabulated below
(Table 1.1):
16
Anhydrides long cure cycles at low exotherm; good composites; castings;
high temperature thermal (high potting;
(200 _C) Tg), mechanical, encapsulation
electrical properties;
With DGEBA-type resins, Primary & secondary polyamines have good room
temperature cures Aliphatic amines react with cycloaliphatic resins only at high
temperatures & in presence of accelerators such as tertiary amines or bisphenol-A.
Chemical modification to yield epoxy adducts by reaction with epoxy groups creates
products with better h&ling functions. For example, in the presence of water
diethylenetriamine (DETA) readily reacts with ethylene oxide to produce a mixture of
mono- & dihydroxyethyl diethylenetriamine with a longer shelf life & less
dermatitic/skin effects than free DETA. (Scheme 1.7)
17
Scheme 1.7
Resinous adducts are synthesized by reaction of excess diamine with epoxy resin.
(Scheme 1.8) Those adduct which have a lower vapour pressure than the diamine,
reduces the odour.
O O
OH OH
Scheme 1.8
An adduct having higher molecular weight yields a more desirable ratio of resin to curing
agent & lower water absorption on curing. The processability of an epoxy-composite
system is improved in case of adduct. For example, the solubility of diaminodiphenyl
sulfone (DDS) is very poor in multifunctional epoxy resins. But DDS epoxy adduct70 has
improved solubility of hardener in the epoxy resin & thus reducing processing
difficulties. The adduct functions as a solubilising agent for the free amine, although the
epoxy adduct contains 20-35% DDS,
Scheme 1.9
18
Polyamides as curing agents are versatile, inexpensive, have little colour, & can be mixed
in any ratio & cure under mild conditions. They exhibit readily workable pot lives &
provide good mechanical properties,. They are primarily used in coating formulations.
Amidoamines are similar to polyamides, but are of lower viscosity. They are synthesized
by the reaction of tall-oil fatty acid with a mono functional-amine such as DETA,
forming an imidazoline structure. (Scheme 1.10)
O
R C N
NH2CH2CH2 N CH2
CH2
H2O
Scheme 1.10
Aromatic amines react slowly with epoxy resins at RT, and need elevated curing
temperatures. Aromatic amines provide better chemical- & thermal- resistance properties
than aliphatic amines. 4, 4’-Diaminodiphenylsulfone (DDS), 4, 4’-
Diaminodiphenylmethane (DDM), & m-phenylenediamine, are the principal
commercially available aromatic amines. To improve on the formers solubility, liquid
eutectic blends of diaminodiphenylmethane & m-phenylenediamine are synthesized
commercially. The commercially availablepolyamine curing agents are given in Table
1.2.
Structure Name
Aliphatic
Cycloaliphatic
1, 2-diamino cyclohexane
19
H 2N (DAC)
H2N
H2N
N-aminoethylpiperazine
N NH
(AEP)
Aromatic
H2N S NH2
O
4,4’-diaminodiphenylsulfone
(DDS)
m-phenylene diamine
H2N NH2
o molecular weight,
1.4.2 Anhydrides
Various type of structurally different anhydrides are used as epoxy curing agents. The
most significant commercially available anhydrides are based on a cycloaliphatic
structure (Table 1.3).
20
Table 1.3: Commercial Anhydride Curing Agents
Name Structure
Phthalic anhydride O
Tetrahydrophthalic anhydride O
O
Hexahydrophthalic anhydride
O
CH3
Nadic methyl anhydride O
Optimum properties are achieved by curing at higher temperatures. The most effective
catalysts for reducing the curing time are tertiary amines such as benzyldimethylamine,
dimethylaminophenol, tris(dimethylaminomethyl) phenol, boron trihalide complexes, &
substituted imidazoles.
21
Epoxy-anhydride systems have low exothermic heats of reaction, low viscosity, longer
pot life, & little shrinkage when cured at higher temperatures. Good mechanical &
electrical properties are shown by the cured system & are used in electrical-casting &
filament-wound epoxy pipe applications. They have imrpoved thermal stabilities
compared to similar amine-cured systems. Anhydrides are the principal hardeners for
cycloaliphatic & epoxidized olefin resins.
1.4.3 Polyimide
Aromatic polyimides71-73 find use for a myriad of applications due to their outstanding
mechanical, electrical & thermal properties. However, hindrances exist in the use of
polyimides as tougheners, as they are not miscible with epoxy resin. Copolyimides have
also been developed to improve solubility & macroscopic properties. More particularly,
the invention is of significance to those epoxy resin compositions, which are curable at
ambient temperatures. Polyimides when based on all aromatic ring structures provides
improved high temperature resistance as well as increased chemical & solvent resistance,
to cured epoxy resin systems. Unfortunately, the only drawback is that they are generally
high melting solids which are not soluble to any appreciable extent in common solvents
or epoxy resins & thus are difficult to incorporate in epoxy resins except at higher curing
temperatures and curing cycles.
The choice of curing agent depends on curing conditions, processing methods & the
physical & chemical properties desired.
22
Hardeners are either catalytic or co-reactive. A catalytic hardener functions as an initiator
for epoxy resin homo-polymerization, whereas the co-reactive hardener acts as a co-
monomer in the polymerization process (Scheme 1.11 & 1.12). The hardeners can react
with the epoxy & pendant hydroxyl groups on the resin backbone by way of either an
anionic or cationic mechanism.
The functional groups adjacent to the epoxy resin also affect the curing process74, 75
.
Electron-withdrawing groups surrounding the epoxy ring often enhance the reactivity of
epoxy resin to nucleophilic reagents, retarding its reactivity toward electrophilic
reagents74, 76,77
.
The epoxide ring is susceptible to attack from chemicals with various structures,
epecially, those co-reactive curing agents with active hydrogen atoms, mainly, alcohols,
thiols, phenols, primary & secondary amines, & carboxylic acids.
R3N
Catalytic: (n + 1) CH CH2 R3N+ CH2CH OCH2CH O-
n
O
Scheme 1.11
Lewis bases contain an unshared pair of electrons in outer orbitals and react with areas of
low electron density. When epoxy resins are cured with primary or secondary amines,
tertiary amines are formed, which then acts as a catalyst for homopolymerization as
shown in reaction scheme 1.7.
23
Glycidyl amines such as triglycidyl-p-aminophenol (XVI) & tetraglycidyl methylene
dianiline (XVII) contain built-in tertiary amines in the resin backbone. Compared to
nitrogen-free multifunctional epoxy resins78, these epoxy resin systems are less thermally
stable.
The curing rate of epoxy resins with tertiary amines is dependant upon the sterical
hindrance of nitrogen. The homopolymerization reaction depends on the
Tertiary amines are primarily used as accelerators for other curing agents, e.g.,
benzyldimethyl amine & 2,4,6-tris(dimethylaminoethyl) phenol in the curing of
anhydride- & dicyanamide-epoxy based systems.
Imidazoles also have both a secondary & a tertiary amine functional group & are mainly
used as both curing agent & accelerator79.
Contrary to Lewis bases, Lewis acids, have an empty outer orbital & look to react with
areas of high electron density. For example, Boron trifluoride, BF3, a corrosive gas, reacts
very easily with epoxy resins, causing gelation within few minutes. But complexing
boron trihalides with amines enhances the curing action.
Various mechanisms have been proposed for hardening epoxy resins with BF3 complexes
or salts80-82. Thermal dissociation of BF3.amine complex may result a proton that further
reacts with the epoxy group to initiate the curing process81. A mechanism, more
consistent with the available data, assumes an amine adduct or salt is solvated by the
epoxy groups, forming an oxonium ion82. The curing reaction is initiated & propagated
by attack of other epoxy groups on the oxonium ion.
24
CH CH2
O OH OH
CH OH
CH2
CHCH2 NRN CH2CH
OH CH2 OH
CH OH
Scheme 1.12
The most widely used agents for epoxy resins as shown in the reaction scheme 1.12 are
Primary & secondary amines83
Reaction of epoxy group with a primary amine initially produces a secondary alcohol & a
secondary amine. Initially curing with a secondary amine affords a tertiary amine & a
secondary alcohol. No competitive reaction is detectable between a secondary hydroxy
group in the backbone & an epoxy group to afford an ether84, 85, provided a stoichiometric
equivalent or excess amine is maintained. However, the secondary hydroxyl groups
formed gradually add to the epoxide groups86, with excess epoxy resin (Scheme 1.13). It
has been researched that primary amines react twice as fast as secondary amines87.
O
OH R CH2 CH OH
Scheme 1.13
25
alcohols are poor accelerators. Reactivity of the system is proportional to hydroxyl
functionality. The best results are achieved with poly-functional alcohols
O O+ OH
R' R' R'
NH CH2 CH HOR" N N CH2 CH
CH2 CH HOR"
R R R
H
Scheme 1.14
The basicity of Aromatic amines is lower than aliphatic amines. For example, the latter
cures epoxy resins at room temperature without accelerators, whereas aromatic amines
require higher hardening temperature. However, with the help of accelerators, the
hardening rates of aromatic amines can approach those of aliphatic amines. On the other
hand, because of the higher acidity of aromatic amines, they react faster than the aliphatic
amines with cyclo-aliphatic epoxy resins. The overall rate of reaction of an amine with
epoxy resin is influenced by the steric hindrance & the electron-withdrawing or electron-
donating groups surrounding the amine. The rate of reaction is lower; if larger the
groups’ are surrounding the amine. This is because electron-withdrawing groups diminish
the nucleophilic character of the amine & lower the reaction rate.
(ii) Mercaptans
Especially at low temperatures, the epoxy-mercaptan reaction is faster than the epoxy-
amine reaction,. It is accelerated by primary & secondary amines. The reaction rate
increases on Increasing the basic strength of the amine. (Scheme 1.15)
O OH
RSH CH2 CH2 RS CH2 CH2
Scheme 1.15
(iii) Isocyanates
26
Isocyanates react with the epoxy resin (Scheme 1.16) to form an oxa-zoldone structure
(by reacting with epoxy group) or with a hydroxyl group (Scheme 1.17) to yield a
urethane linkage. A cross-linked system is achieved from a di- or polyfunctional
isocyanate & a polyepoxide90.
O CH2
R N C O CH2 CH CH N R
O C
Scheme 1.16
R N C O CH2 CH CH2 CH
OH O C NHR
Scheme 1.17
Between the two chemically reactive functional groups in an epoxy resin viz., epoxy &
hydroxyl groups; as the molecular weight of DGEBA resins increases, the epoxy content
decreases, while the hydroxyl content increases. Urea-formaldehyde, Melamine-
formaldehyde, & phenol-formaldehyde resins form cross-linked networks by reacting
with hydroxyl groups of high molecular weight epoxy resins.
27
OH OH OH
O
n OH
OH
OH O CH2 CH O CH2 CH
CH2 CH 2
Scheme 1.18
Poly-carboxylic polyesters were known as curing agents for epoxy powder coatings from
1970’s, but have not found widespread use. The chemical reaction between a carboxylic
acid & an epoxy resin is depicted below (Scheme 1.19):
OH
OH OOCR
OH OCH2CHCH2
O OH
OH
Scheme 1.19
28
The first reaction produces a beta-hydroxypropyl ester, which reacts with a second mole
of carboxylic acid to form a diester. The hydroxypropyl esters also undergo
polymerization by reacting with secondary hydroxyl group of epoxy.
Both esterification & etherification occur during the uncatalyzed reaction of epoxy resins
with an acid dianhydrides which occurs slowly even at 200oC91, 92; the chemical reaction
is depicted below. Secondary alcohols present in epoxy backbone react with anhydride to
form a half ester, which reacts with epoxy group to give diester. A side-reaction is that
with a secondary alcohol, either on the resin back-bone or formed during the
esterification, resulting in a β-hydroxy ether. Basic catalysts favour esterification
(Scheme 1.20).
O O CH2
R R O
CH2 CH
O
CH OH
OH
R R
O O
half ester
O CH2 O CH2
R O R O CH
CH O
H2C CH
OH OCH2CH
R R
O O OH
CH2 O CH2
CH OH H2 C CH CH O CH2 CH
OH
Scheme 1.20
The characterization of liquid Epoxy resins is mainly verified by epoxy content, color,
density, viscosity, hydrolysable chloride & volatility. The less significantly analyzed are
29
glycol content, total chloride content, ionic chloride, & sodium. Whereas, Solid epoxy
resins are characterized by epoxy content, melting point, solution viscosity, color, &
volatility. The Less significantly quoted are phenolic hydroxyl content, ionic chloride,
sodium, hydrolysable chloride, & esterification equivalent.
The epoxy content of liquid resins is expressed as epoxide equivalent weight (EEW) or
weight per epoxide (WPE), and defined as the weight (grams) that contains 1 g
equivalent of epoxide. The analysis of epoxy content of liquid resins & solid resins is
commonly carried out by titration of the epoxide ring by hydrogen bromide in acetic
acid93.
High viscosity liquid epoxies prevent good mixing with curing agents, resulting in non-
homogeneous mixtures, incomplete network formation, & poor performance. On the
other hand, too low viscosity would affect application characteristics such as coverage &
appearance. Viscosities of liquid resins are typically measured with a Cannon–Fenske
capillary viscometer at 25oC, or a Brookfield viscometer. The viscosity of the epoxies is a
function of the temperature & Hydrolysable Chloride (HyCl) content of liquid.
The cured epoxy performance is affected by the epoxy curing process. Thus, to obtain
optimum network structure & performance, it is imperative to understand the curing
process & kinetics to design an optimal cure schedule. It is very important to understand
the reactivity of different curing agents towards the epoxy structure to develop a proper
curing process,.
Cured epoxy thermosets are more difficult for analysis than thermoplastics since they are
insoluble & generally intractable. So such systems must be evaluated by considering all
variables affecting performance. However, the properties are influenced by factors at the
molecular level, such as
o nature of the covalent bond developed between the epoxy resin & the curing agent
during cross-linking; &
30
The di-functional DGEBA resins are available commercially in a wide range of
molecular weights. As the resin molecular weight increases, the cross-link density of
difunctional resin cured by way of epoxy group decreases. For high molecular weight
resins, they are frequently cured via the secondary hydroxyl group.
The degree of cure is measured by the extent of cross-linking & the most favoured
properties are obtained by highest cross-linking. The ultimate cross-link density is
strongly influenced by the curing temperature and the post-cure property influenced is the
increase in chemical resistance.
The transformation from sol to gel to glass has been measured by a variety of
techniques94, such as viscosity95, calorimetry93, dielectric96, 97 & mechanical relaxations98,
99
, dilatometry99 & ultrasonic measurements100. Several spectroscopic methods including
infrared101, 102 & Raman spectroscopy103, 104, nuclear magnetic resonance105, electron
paramagnetic resonance106, fluorescence107, Brillouin scattering108 & photon correlation
spectroscopy100 have also been used. Amongst all the techniques described above, DSC
has been used widely to study kinetics & mechanism of curing epoxy resins.
31
The structure & reactivity of the curing agent plays an important role in controlling the
curing reaction of epoxy resin. The curing exotherm onset is primarily dependant on the
nucleophilicity of the amino group. Aromatic amines having electron donor substituents
start the epoxy resin curing at lower temperatures & also have lower activation energy
134
.
The relative reactivities135-138 of diamines were as follows: DDS < 3, 3’- DDS < DDM
This is because of due to the presence of sulfone group which is electron withdrawing,
the nucleophilic character of amino group is decreased, resulting in delay of curing
136
exotherm. The electron transfer due to resonance is more predominant for DDS
Whereas, DDM is more reactive than DDS because the methylene group acts an electron
donor.
Other factors which affect the cure evolution & final properties are
o cure extension
The structure of the hardener greatly affects the thermal stability. As measured by
thermogravimetric analysis (TGA), the heat resistance of aliphatic amines is low,
whereas, Anhydride systems, at temperatures well below its main decomposition point of
392oC, tend to separate off the anhydride backbone.
The resin to hardener ratio has a very strong impact on the structure of the cured resin &
its properties139. A wide variety of products is obtained by changing the ratios. The
products range from an amine-epoxy adduct with excess amine to an epoxy-amine adduct
with excess epoxy. Theoretically, when equal molar quantities of resin & hardener are
combined, a cross-linked thermoset polymer structure is achieved.
32
elimination of water (dehydration) preceded by chain scission. The source of water is
Dehydration and is the major gas evolved on heating epoxy formulations140-144. Further
Epoxy decomposition depends on the nature of the dehydrated structure. The presence of
such unsaturations is indicated by appearance of 1650 cm-1 band in IR145-148. They are
responsible for weakening the aliphatic C-O or C-N bonds in the β position. The
calculated energy of these allylic bonds is is lower than the energy of other bonds in the
cured epoxy network, approx 290 & 270 kJ/mol, respectively. By thermal decomposition
of the weak C-O bonds, phenolic chain ends are formed, whereas from the scission of C-
N bonds, secondary amine terminal functions result. Cyclic chain structures, may also be
formed simultaneously, and are favoured due to the reduced mobility of macroradicals in
the solid matrix. If scission of C-O &/or C-N bonds occurs before dehydration of
secondary alcohols, organic products such as acetone are also formed. The volatilization
of DGEBA in these reactions is a result of the fact that DGEBA is difunctional, therefore
repetition of the reactions on the same units leads to loss of corresponding DGEBA units
from the residue149.
The chemicals in epoxy resin systems can impact your well being if they interactwith
skin, or when they evaporate or form a mist or dust in the air you breathe. The key
aftereffects of overexposure are irritation of the eyes, nose, throat, & skin, skin allergies,
& asthma. The solvent additives could cause other effects such as for instance headaches,
dizziness, & confusion.
(A)Lungs: Vapors & spray mists of all epoxy resin system chemicals can irritate lungs.
Some individuals develop asthma from the curing agents. ApparentSymptoms of asthma
include chest tightness, shortness of breath, wheezing, & coughing. These symptoms may
occur after work or at night. Once an individual becomes allergic to curing agents, even
the dusts from sanding or grinding the hardened plastics can cause an asthma attack.
(B) Skin: Epoxy resins can cause skin irritation. Symptoms include redness, swelling,
shedding, & itching on the hands, experience, or other regions of contact. Some
individuals create a skin allergy or sensitivity to epoxy resins or mists. Skin allergies may
possibly build following only a few days of contact or following many years of exposure
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to epoxies. Sensitized skin may become red, inflamed, blistered, & itchy actually from
brief connection with epoxy resins.
(C) Eyes, Nose, & Throat: Most epoxy resin system compounds & their vapors
(especially the hardeners & solvents) may worsen eyes, nose, & throat. Some individuals
build headaches consequently of the irritation. If the fluids are splashed in to eys they'll
sting, & they can seriously injury the eye. In case there is vision contact, immediately
wash the eyes with water. Keep on rinsing for fifteen minutes & then find medical
attention.
(D) Nervous System: Solvents consumed or absorbed through your skin can affect main
nervous program exactly the same way consuming alcohol does. Apparent symptoms of
solvent overexposure contain head-aches, vomiting, dizziness, slurred presentation,
distress, & loss in consciousness.
(E) Reproductive System: Epoxy resins & hardeners themselves possibly don’t affect
pregnancy & reproductive cycle in humans. However, a number of the diluents &
solvents in epoxy resin methods might affect reproduction. Two solvents sometimes
within epoxy resin systems (2-ethoxyethanol & 2-methoxyethanol) cause birth problems
in laboratory animals & decreased sperm counts in men. Some glycidyl ethers also harm
the testes & cause birth problems in test animals. It is unknown whether they've the same
results in humans. Other solvent ingredients have not been adequately tested to find out
when they affect reproduction. However, we do understand that solvents inhaled by a
woman can reach a developing foetus & might contaminate the breast milk. They could
affect the child only as they affect the mother. We recommend that pregnant & nursing
women reduce their exposure to solvents, just like they should reduce their exposure to
liquor150.
The applications for epoxy-based materials are extensive & include coatings, adhesives &
composite materials such as for instance those using carbon fibre & fibreglass
reinforcements (although polyester, vinyl ester, & other thermosetting resins are also
used for glass-reinforced plastic). The chemistry of epoxies & the range of commercially
available variations allow cure polymers to be produced with a really broad range of
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properties. Generally, epoxies are noted for their excellent adhesion, chemical & heat
resistance, good-to-excellent mechanical properties & very good electrical insulating
properties. Many properties of epoxies can be modified (for example silver-filled epoxies
with good electrical conductivity are available, although epoxies are generally electrically
insulating). Variations offering high thermal insulation, or thermal conductivity coupled
with high electrical resistance for electronics applications, are available151,152.
1.9.1 Adhesives
Epoxy adhesives are a major area of the class of adhesives called "structural adhesives"
or "engineering adhesives" (that includes polyurethane, acrylic, cyanoacrylate, & other
chemistries.) These high-performance adhesives are utilized in the construction of
aircraft, automobiles, bicycles, boats, golf clubs, skis, snowboards, & other applications
where high strength bonds are needed153,154. Epoxy adhesives could be developed to
match nearly every application. They may be used as adhesives for wood, metal, glass,
stone, & some plastics. They could be made flexible or rigid, transparent or
opaque/colored, fast setting or slow setting. Epoxy adhesives are better in heat &
chemical resistance than other common adhesives. Generally speaking, epoxy adhesives
cured with heat could be more heat- & chemical-resistant than those cured at room
temperature. The potency of epoxy adhesives is degraded at temperatures above 350 °F
(177 °C). Some epoxies are cured by exposure to ultraviolet light.Such epoxies are
commonly utilized in optics, fibre optics, & optoelectronics.
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Two part epoxy coatings were developed for high quality service on metal substrates &
use less energy than heat-cured powder coatings. These systems make use of a 4:1 by
volume mixing ratio, & dry quickly providing a hardcore, protective coating with
excellent hardness. Their low volatility & water cleanup makes them helpful for factory
cast iron, cast steel, cast aluminium applications & reduces exposure & flammability
issues associated with solvent-borne coatings. They're usually utilized in industrial &
automotive applications being that they are more heat resistant than latex-based & alkyd-
based paints. Epoxy paints often deteriorate, called chalk out, as a result of UV exposure.
Polyester epoxies are employed as powder coatings for washers, driers & other "white
goods ".Fusion Bonded Epoxy Powder Coatings (FBE) are extensively employed for
corrosion protection of steel pipes & fittings utilized in the oil & gas industry, potable
water transmission pipelines (steel), concrete reinforcing rebar, etc. Epoxy coatings will
also be popular as primers to boost the adhesion of automotive & marine paints especially
on metal surfaces where corrosion (rusting) resistance is important. Metal cans &
containers tend to be coated with epoxy to stop rusting, specifically for foods like
tomatoes which can be acidic. Epoxy resins will also be employed for high performance
& decorative flooring applications especially terrazzo flooring, chip flooring & colored
aggregate flooring155,156.
1.9.3 Composites
Epoxies may also be used in producing fibre-reinforced or composite parts. They are
more costly than polyester resins & vinyl ester resins, but usually produce stronger &
more temperature-resistant composite parts. Epoxy resins are suitable as a fibre-
reinforcing material since they exhibit excellent adhesion to reinforcement, cure with low
shrinkage & provide good mechanical, electrical & thermal-, chemical-, fatigue-, &
moisture-resistant properties.
The processes for making composites encompass the whole range of epoxy resin
technology, i.e., laminating, filament winding, pultrusion, casting, & moulding. For their
excellent adhesion, good mechanical properties, & resistance to humidity & chemicals,
epoxy resins are employed in combination with glass, graphite, & boron & Kevlar fibers.
The orientation of the fibers is important in establishing the properties of the laminate.
Unidirectional, bidirectional, & random orientation are possible. The characteristics of
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the cured resin system are really important because it must transmit the applied stresses to
each other. The critical point in a composite may be the resin-fibre interface. The
adhesive properties of epoxy resins cause them to become especially suited to composite
applications.
In casting, a resin-curing agent system is charged right into a specially designed mould
containing the electrical element of be insulated. After cure, the insulated part retains the
design of mould. In encapsulation, an attached electronic component like a transistor or
semiconductor in a mould is encased in an epoxy resin-based system. Coil windings,
laminates, lead wires, etc, are impregnated with the epoxy system. Both DGEBA &
cycloaliphatic epoxy resins are utilized in casting systems. The cycloaliphatic resin
systems exhibit good tracking properties153 & better resistance than DGEBA resins to
UV radiations, that causes crazing & surface breakdown. Amine curing agents are
utilized in small castings & anhydrides in large castings. Transfer moulding can be used
to encapsulate the solid-state devices such as for example diodes, transistors & integrated
circuits in epoxy moulding powders. In the manufacture of tools, epoxy casting resins are
utilized as prototype & master models for product design, drilling & welding jigs,
checking fixtures, vacuum forming & injection moulding, foundry patterns & stretch
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blocks. They're less expensive than metals & can be modified quickly & cheaply. They
provide high dimensional stability, low shrinkage, & good mechanical properties. Simple
casting & hand layup laminating techniques are employed159,160.
There are two main regions of marine use. Because of the better mechanical properties in
accordance with the more common polyester resins, epoxies are useful for commercial
manufacture of components where a high strength/weight ratio is required. The next area
is that their strength, gap filling properties & excellent adhesion to numerous materials
including timber have created a boom in amateur building projects including aircraft &
boats. Normal gelcoat formulated for use with polyester resins & vinylester resins doesn't
stick to epoxy surfaces, though epoxy adheres very well if applied to polyester resin
surfaces. "Flocoat" that is normally used to coat the inside of polyester fibreglass yachts
can also be suitable for epoxies161-163.
Epoxy materials tend to harden somewhat more gradually, while polyester materials tend
to harden quickly, especially if lots of catalyst is used. The chemical reactions in both
cases are exothermic. Large quantities of mix will create their own heat & greatly speed
the reaction, so it is usual to mix small amounts which can be used quickly.
While it is common to associate polyester resins & epoxy resins, their properties are
sufficiently different that they're properly treated as distinct materials. Polyester resins
are typically low strength unless used in combination with a reinforcing material like
glass fibre, are relatively brittle unless reinforced, & have low adhesion. Epoxies, in
comparison, are inherently strong, somewhat flexible & have excellent adhesion.
However, polyester resins are much cheaper. Epoxy resins typically require an exact mix
of two components which form a third chemical. With regards to the properties required,
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the ratio might be anything from 1:1 or higher 10:1, in every case they should be mixed
exactly. The final product is then the precise thermo-setting plastic. Until they are mixed
both elements are relatively inert, even though the'hardeners'are generally more
chemically active & should really be protected from the atmosphere & moisture. The rate
of the reaction can be changed by using different hardeners, which may change the type
of the last product, or by controlling the temperature. By comparison, polyester resins
usually are made available in a'promoted'form, in a way that the progress of previously-
mixed resins from liquid to solid is underway, albeit very slowly. The only variable
offered to the user is to alter the rate of this method employing a catalyst, often Methyl-
Ethyl-Ketone-Peroxide (MEKP), which is very toxic. The clear presence of the catalyst in
the last product actually detracts from the desirable properties, in order that small
amounts of catalyst are preferable, so long as the hardening proceeds at a satisfactory
pace. The rate of cure of polyesters can therefore be controlled by the amount & kind of
catalyst along with by the temperature.
As adhesives, epoxies bond in three ways: a) Mechanically, since the bonding surfaces
are roughened; b) By proximity, since the cured resins are physically so near the bonding
surfaces that they're hard to separate your lives; c) Ionically, since the epoxy resins form
ionic bonds at an atomic level with the bonding surfaces. This last is substantially the
strongest of the three. By comparison, polyester resins can only bond utilising the first
two of those, which greatly reduces their utility as adhesives & in marine repair.
Epoxy adhesives really are a major the main class of adhesives called "structural
adhesives" or "engineering adhesives" (that includes polyurethane, acrylic, cyanoacrylate,
& other chemistries.) These high-performance adhesives are found in the construction of
aircraft, automobiles, bicycles, boats, golf clubs, skis, snowboards, & other applications
where high strength bonds are required. Epoxy adhesives may be developed to match
nearly every application. They may be used as adhesives for wood, metal, glass, stone, &
some plastics. They may be made flexible or rigid, transparent or opaque/colored, fast
setting or slow setting. Epoxy adhesives are better in heat & chemical resistance than
other common adhesives. Generally speaking, epoxy adhesives cured with heat may well
be more heat- & chemical-resistant than those cured at room temperature. The strength of
epoxy adhesives is degraded at temperatures above 350 °F (177 °C).
39
Some epoxies are cured by exposure to ultraviolet light.Such epoxies are commonly
found in optics, fibre optics, & optoelectronics164,165.
In the aerospace industry, epoxy is employed as a structural matrix material which can be
then reinforced by fibre. Typical fibre reinforcements include glass, carbon, Kevlar, &
boron. Epoxies may also be used as structural glue. Materials like wood, & others which
are 'low-tech' are glued with epoxy resin166,167.
Epoxy resin formulations are essential in the electronics industry, & are employed in
motors, generators, transformers, switchgear, bushings, & insulators. They are excellent
electrical insulators & also protect from dust & moisture. In the electronics industry
epoxy resins are the principal resin used in over molding integrated circuits, transistors &
hybrid circuits, & making printed circuit boards. The largest type of circuit board "FR-4
board" is a sandwich of layers of glass cloth bonded in to a composite by an epoxy resin.
Epoxy resins are acustomed to bond copper foil to circuit board substrates, & really are a
component of the solder mask on many circuit boards.
Flexible epoxy resins are used for potting transformers & inductors. By utilizing vacuum
impregnation on uncured epoxy, winding-to-winding, winding-to-core, & winding-to-
insulator air voids are eliminated. The cured epoxy is an electrical insulator & a better
conductor of heat than air. Transformer & inductor hot spots are greatly reduced, giving
the component a well balanced & longer life than un-potted product168,169.
Inks & resists comprise a relatively small but high value & growing market for epoxies &
epoxy derivatives. In 2001, there clearly was an estimated of 6800 MT of epoxies &
epoxy derivatives found in this market to create ink & resist formulations worth almost
$400 million in the U.S. market. Epoxies are often used with other resins such as for
example polyester acrylates & urethane acrylates in these formulations. The biggest
applications are lithographic & flexographic ink resist technology is widely found in the
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electronics industry to manufacture printed circuits. The resist (a coating or ink) is
applied over a conducting substrate such as for example copper in a structure to safeguard
its surface during etching, plating, or soldering. Cure is either by radiation or heat. The
uncured coating (or ink) is removed later by solvents. Solder masks perform similar
functions in the manufacturing of printed circuit boards170,171.
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1.10 SCOPE OF THE PRESENT STUDIES
Unmodified epoxies have poor chemical, mechanical & thermal properties. Hence
modification of epoxy resin has been the main topic of research interest since its
discovery. A substantial work has been carried out to boost the properties of epoxy resins.
The effect of structure of cyclic compounds as curing agents on the curing of epoxy resin
has been adequately described in the literature. Since aromatic cyclic compounds are
noted for their high thermal stability, it has created a pursuit to investigate the curing &
thermal behaviour of epoxy resin using amines, anhydrides & benzoxazines having cyclic
aromatic ring.
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