Water Sorption and Solvent Sorption

Behavior of Epoxy/Rubber Polymer Blends

Padmanabhan Krishnan

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Hygrothermal Effect on Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Design Criteria and Hygrothermal Influence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Hygrothermal Conditioning and Evaluation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Theories and Laws of Sorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Diffusion Models and Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Performance and Function After Hygrothermal Attack . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Summary and Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Implications and Suggestions for Further Work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

Abstract
The water and solvent sorption behavior of epoxy/rubber polymer blends of
various structures are discussed in this chapter. The sorption phenomena are
explained in these blends with respect to the surrounding temperature, relative
humidity, and moisture concentration profiles based on parameters like diffusion,
part and laminate thickness, weight gain due to absorption over time, and
saturation equilibration. A reasonable correlation is attempted through Fickian
and non-Fickian absorption models for epoxies, rubbers, their blends, and the
observed properties. A brief note is presented on the viscoelastic models of
environmentally affected blends. The observed changes in the physical, chemical,
mechanical, and electrical properties of the blends are documented. Here again,
distinction is made between the sorption characteristics of solid rubber/epoxy and
liquid rubber/epoxy blends. The hygrothermal performance of fiber composites
fabricated with epoxy/rubber blends as the matrix materials is also discussed and

P. Krishnan (*)
VIT University, Vellore, India
e-mail: padmanabhan.k@vit.ac.in

# Springer International Publishing AG 2016 1

J. Parameswaranpillai et al. (eds.), Handbook of Epoxy Blends,
DOI 10.1007/978-3-319-18158-5_12-1
2 P. Krishnan

presented along with their applications. Limitations, implications, and sugges-

tions for future work have been included at the end of the chapter.

Keywords
Epoxy/rubber blends • Moisture uptake • Solvent sorption • Osmosis • Diffusion •
Concentration profile • Absorption models • Hygrothermal conditioning •
Property degradation

Introduction

The epoxy resins and their hardeners are mixed together to cure in to a highly cross
linked and chemically resistant thermosetting plastic solids (Lee and Neville 1967).
Their functionality and the presence of initiators, other catalysts, and diluents
determine their hardness, strength, stiffness, and above all their toughness, i.e.,
resistance to crack initiation and propagation. Epoxy matrices are basically brittle
in nature, higher the functionality more the brittleness. Hence, tetrafunctional epoxy
resins cured with anhydrides or tetramines are more brittle than their difunctional
counterparts. This general drawback of epoxy systems is often countered by blend-
ing them with tougher materials like liquid rubber, thermoplastics, solid rubbers, and
particulate fillers (Garg and Mai 1988).
In order to retard matrix cracking of epoxy systems in various service applica-
tions, liquid rubbers are often added up to 15 phr (parts per hundred resin) in the
mixtures of epoxies and catalysts and homogenized thoroughly before phase sepa-
ration occurs (Gabriel and Advani 2003). Solid rubber particles are also added
instead of liquid rubbers if a tighter control over rubber particle size distribution
and the fracture properties is required (Padmanabhan 2015). EPDM (Ethylene
Propylene Diene Monomer) rubbers are also used as solid particulates to impart
toughness in epoxy systems as their atmospheric and weathering resistance is also
excellent (Blow and Hepburn 1982). This enables the use of such rubber toughened
epoxies for long-term service life–oriented applications where mechanical property
degradation over the life span is comparatively within the acceptable limits.
Epoxies or “Epi oxygen” positioned DGEBA (Diglycidyl Ether of BisPhenol A)
can be cured in many ways in to solid networked polymers. They can be anhydride
cured giving rise to copolymers, catalytically cured using BF3 amine complexes
leading to ring opening polymerization of the terminal epoxide groups or amine
cured that generates hydroxyl groups. Here, the BF3 amine group cured molecules
are terminal in polymerization and have very low moisture concentrations at equi-
librium. In the case of amine cured epoxies, the hydroxyl groups act as polar centers
for hydrogen bonding with molecules of absorbed moisture. Depending on the type
of the amine group, i.e., whether it is primary, secondary, or tertiary, variations in
moisture concentrations and deviations from Fickian diffusion behavior can occur
(Pritchard 1999). To appraise the young reader on what it means, we transport
ourselves to 1855, when physiologist Adolf Fick first reported (Fick 1855a) his
now-well-known laws governing the transport of matter through matter by diffusive
Water Sorption and Solvent Sorption Behavior of Epoxy/Rubber Polymer Blends 3

means. Fick was inspired by the earlier experiments of Thomas Graham, which were
rather incomplete as no laws could be deducted from his work. The Fick’s law is very
much analogous to the relationships discovered by other eminent scientists. Darcy’s
law on hydraulic flow, Ohm’s law on charge transport, and Fourier’s Law on heat
transport were the other laws that were laid down around the same epoch that dwelt
on some form of transport or the other.
Depending upon their functionality, viscosity, wettability, moisture, and fluid
uptake susceptibilities, epoxy systems are used in mechanical, aerospace, consumer,
civil and electronic applications as adhesives, sealants, laminating resins, fillers,
matrix materials, encapsulants, and boards.
The types and varieties in rubber utilized for blending with other plastics are large
(Blow and Hepburn 1982). Though latex natural rubber and synthetic rubbers like
SBR (Styrene Butadiene Rubber), Butyl, Nitrile, Stereoregular polymer rubbers,
Ethylene propylene rubbers, Fluorocarbon rubbers, Silicone rubbers, Nylon rubbers,
Chloroprene rubber, (ABS) Acrylonitrile Butadiene Styrene rubbers, Polyurethane
rubbers, Neoprene, Isoprene, and vulcanized rubbers are currently in the market,
only a handful of them are blended along with epoxies for obtaining the required
properties and service life.
Rubbers require certain traits to be compatible with epoxies. Liquid rubbers go
through a phase separation and cannot be added more than say about 15 phr in an
epoxy/hardener system as then they would be the majority matrix materials
causing deterrence in strength and stiffness. Open ended molecular systems with
ionic, polar, and unsaturated liquid structures are mandatory for blending with
epoxies in order to have good bonding but are moisture prone as they are open
ended and susceptible to hydrogen and hydroxyl bond formations. Among rubbers,
fluorocarbon rubbers, ABS rubbers, EPDM rubbers, and nitrile rubbers with high
acrylonitrile content are fairly moisture and oil resistant. Epoxies are normally
blended with carboxyl terminated, hydroxyl terminated, or amine terminated
butadiene rubbers as it is believed that termination provides fewer avenues for
moisture and fluid ingress. The CTBN (Carboxyl Terminated Butadiene Rubber)
blended epoxies are very popular with those in the carbon fiber prepreg or the
preimpregnated fiber/epoxy manufacturing trade as the epoxy-rubber blend pro-
vides for high fracture toughness even under conditions of hygrothermal attack –
meaning combined attack of moisture and temperature (Thomas 2014). The
isobutylene-isoprene rubbers have moderate to high moisture resistance and can
be blended with epoxies.
Commercially many epoxy and modified epoxy systems are available for com-
posite applications. (www.Cytec.com; www.hexcel.com; Ciba-Geigy Datasheet
1983, 1984). As some of the rubber modified epoxies are more susceptible to
moisture absorption than the epoxies themselves, it becomes important to measure
their moisture saturation equilibrium to evaluate their impact on the mechanical
properties. Table 1 provides basic information about the moisture content at satura-
tion for epoxies and modified epoxies (Lee 1989). Some of the rubber toughened
epoxies are also listed for their moisture susceptibility. It is to be understood that a
long-term moisture saturation of 1–3 wt% is considered good, a range between 3.1
4 P. Krishnan

Table 1 Moisture absorption at saturation for epoxies and modified epoxies

Material Moisture absorption at saturation
supplier Designation Polymer type (Wt%)
Shell 9101 Epoxy 2
Union 4901A Epoxy 7.2
Carbide (MDA)
Hercules 2220-1 Toughened epoxy 3.8
Hercules 2220-3 Toughened epoxy 4
Am. 907 Multiphase epoxy 5.1
Cyanamid
Fibredux 914 Rubber toughened epoxy 7
Hexcel F155 Rubber toughened epoxy 9.4
(250
F)

and 7.5 wt% is considered average, and anything beyond 7.5 wt% is not acceptable
in sensitive industries like aerospace.

Hygrothermal Effect on Structure

Polymers are prone to absorb moisture over time and become swollen and plasticised
that deter their mechanical and electrical function. As water is electrically and
thermally conducting, these properties change with time once a polymer is put into
service. For a detailed data and understanding of the moisture, oil, acid, alcohol, and
alkali attack including the weathering behavior of polymers and elastomers, the
reader is directed to the works of Billmeyer (2015). To know the influence of
hygrothermal attack on the mechanical, chemical, and bio-medical properties of
polymeric composites a thorough knowledge of equilibration saturation condition-
ing and diffusion kinetics is required (Padmanabhan 2006, 2009). Another investi-
gation explains the influence of marine environment on the durability of plastics and
reinforced plastics (Pritchard 1999). As the temperature of moisture conditioning
increases up to 100
C the moisture concentration at equilibrium also increases as
due to swelling and micro-cracking moisture uptake shows a rise in the concentra-
tion level. Void content, resin type, temperature, stress levels, presence of flaws,
cracks, and spiking have a pronounced effect on moisture absorption and fluid
uptake by polymers (Mallick 1994). Adamson has proved a strange but noticeable
reverse thermal effect in the moisture absorption characteristics of cast epoxy
systems where the susceptibility increased with a sudden drop in the temperature
(Adamson 1983).
Hydrolysis of cured epoxies is discussed in detail by Powers (2009). However,
the chemistry of water reaction with cured epoxy blends has not been well investi-
gated. The “epi” oxygen at the center of CH2 and CH bonds that lead to the epoxy
signature nomenclature open up and form hydroxyl bonds due to the reaction with
Water Sorption and Solvent Sorption Behavior of Epoxy/Rubber Polymer Blends 5

Glassy region
Dry
Wet
Strength/Stiffiness

Increasing moisure content

Rubbery region

Tgw Tgo
Temperature

Fig. 1 A schematic illustration of Wet Tg forming with moisture content

moisture or water. Certain other organic compounds are also capable of hydrolyzing
epoxies and their blends.
As the epoxies possess higher Tg (Glass Transition Temperatures) than the
rubbers in their blends, the Tg of the blends are in between that of the rubber and
the epoxy. To make things worse, the wet Tg of the blends after moisture saturation
equilibrium is attained gets lowered from the dry initial Tg due to plasticization and
nonlinear viscoelasticity setting in (Gibson 1994; Chamis and Sinclair 1982;
Padmanabhan 2016). The relationship between dry Tg and wet Tg of plastics in
general is illustrated schematically for moisture saturation conditions, in Fig. 1.
The hygrothermal degradation of the modified epoxy strength or stiffness can be
estimated by using an empirical Eq. 1a, b (Gibson 1994) that is
 
P T gw  T 1=2
Fm ¼ ¼ (1a)
P0 T go  T o

and


T gw ¼ 0:005Mr 2  0:1Mr þ 1:0 T go (1b)

Where,
Fm = Mechanical property retention ratio,
P = Strength or stiffness after hygrothermal degradation,
P0 = Reference strength or stiffness before degradation,
T = Temperature at which P is to be predicted (
C),
Tgo = Glass transition temp. for reference dry condition,
Tgw = Glass transition temperature for reference wet condition at moisture con-
tent corresponding to property P,
6 P. Krishnan

Moisture Concentration Profiles

6

5 15 Yr
8 Yr
5 Yr
Weight Gain - Percent

4 2 Yr
1 Yr
22 Weeks
3 18 Weeks
1 Week

0
0 0.05 0.01 0.15 0.2 0.25 0.3
Distane into plate (inch)

Fig. 2 Time variable moisture concentration profiles across the thickness of a typical epoxy resin
plate at 100
F and 100% RH

To = Test temp. at which Po was measured (25
C),

Mr = Weight percent of moisture at equilibrium.
Figure 1 depicts lowering of the Tg in wet conditions and that of the mechanical
properties attained after equilibration due to moisture or fluid ingress. It must be
stated that generally accelerated or humidity chamber conditioning at room or an
elevated temperature is carried out between 50% and 100% RH (Relative Humidity)
conditions. Many recommended combinations of temperature and RH are practiced
for understanding the influence of hygrothermal attack on epoxies, modified epoxies,
and composites (ASTM 5229M 1998). Many investigators have estimated the
moisture concentration profiles across part or specimen thicknesses for thin and
thick sections based on parameters like diffusivity, moisture concentration, diffusion
coefficient, concentration gradient, time, and temperature. Figure 2 depicts one such
investigation where the weight gain due to absorption over time is illustrated for
conditioning at a fixed temperature and RH from few days to years for an epoxy resin
specimen with a fixed thickness.
In amorphous materials like epoxy-rubber blends, diffusion is characterized by
migration of molecules themselves. The structure is characterized by very strong
covalent primary bonds which hold the molecules together and by much weaker
secondary bonds between the molecules. Diffusion here is analogous to interstitial
diffusion. If the polymer is bulky and heavily networked as in the present case,
motion becomes difficult; polymer diffusion rate measurements are often used to
relate to molecular weight determination as there is a relationship between diffusion
Water Sorption and Solvent Sorption Behavior of Epoxy/Rubber Polymer Blends 7

and molecular weight of a polymer. It is interesting to note that the evolution of the
size of a rubber particle vs. its molecular weight has a direct influence on the
diffusion of water through the bulk of it when present as a phase in epoxies. As
the rubber particle size grows in evolution its molecular weight increases and the
susceptibility to moisture diffusion decreases. On the other hand, the susceptibility
of solid rubber additions, like EPDM, is directly related to their structure and has no
bearing on the evolution of a phase from a liquid state in an epoxy blend that is in a
state of curing (Padmanabhan 2015).

Design Criteria and Hygrothermal Influence

For a detailed understanding of the hygrothermal influence on the epoxies,

epoxy–rubber blends, and their composites the reader is referred to the works of
Joseph R. Soderquist. Much of the work is available in the form of reports on aircraft
composite structures as the hygrothermal influence, and its effect on the function of
FRP structures is a decisive factor in the qualification of aerospace polymer com-
posites (Soderquist 1998; MILHDBK-17 and MIL-HDBK- 17B 2002). Parida et al.
have investigated the airworthiness considerations in the type certification of FRP
(Fiber Reinforced Plastics) composites for civil aircraft development with special
relevance to mechanical property degradation after hygrothermal conditioning up to
saturation (Parida et al. 1996). It is noteworthy that only the mechanical property
evaluated after degradation due to hygrothermal saturation needs be considered as
design criteria. The statistical A-basis and B-basis criteria for reliability in the
strength and stiffness data have also been addressed. An A-basis design allowable
of a component has at least a 99% probability of survival with a confidence level of
95%. But a B-basis design allowable of a component possesses only a 90 plus %
probability of survival with a confidence level of 95% (Mallick 1994). It is seen that
a statistical approach is adopted for polymeric and polymer composite materials to
qualify them for critical applications as their mechanical property variability is
higher than metallic materials. Figure 3 gives the moisture weight gain for a neat
epoxy resin as a function of time for different humidity conditions. When many such
samples are conditioned and tested later for mechanical properties, one could
generate the required statistical reliability data.

Hygrothermal Conditioning and Evaluation

Natural aging of epoxy-rubber blends depends on the humidity and temperature

conditions of the real environment. This means a local fluctuation of the daily
temperature and humidity changes over a period of time that are required for
saturation conditioning of the part or component. Random changes in temperature
and relative humidity also cause absorption and desorption on a random scale by and
from the blend. Natural aging is associated with weathering, discoloration, and
degradation of the material which depend upon the randomness of the weather
8 P. Krishnan

Moisture Weight Gain as a Function of Time for Different

Humidity Condition
6

5
Weight Gain (%)

2 100 deg F and 100% RH

100 deg F and 75% RH
1

0
0 2 4 6 8 10 12
Time (Days)

Fig. 3 Moisture weight gain for a typical neat epoxy resin as a function of time for different
humidity conditions

conditions and the material response to it. Natural rubbers in general become brittle
with moisture attack and harden in an epoxy blend. So they tend to embrittle the
structure which is undesirable. The reactions responsible for this are condensation
reaction and hygrothermal curing. Hence, the addition of natural rubbers to epoxies
is never carried out as the synthetic rubbers enhance the toughness even under the
influence of moisture or fluid uptake.
Artificial aging on the other hand is carried out in a humidity or environmental
chamber under set conditions of relative humidity and temperature. The conditions
vary from a cold-dry to a hot-wet setting. Some of the interesting standard practices
for plastics and reinforced plastics are listed here (ASTM D 570 1995; ASTM D
618 1996; ASTM D 696 1991; ASTM D 756 1993; ASTM D 5229/D 5229M 1998).
It must be emphasized here that none of the above standards refer to epoxy-rubber
blends in particular. Some of them, like the D 5229 M, are considered more
applicable. Humidity chambers normally possess temperature ranges of 60
C to
100
C and relative humidity ranges from 0% to 100% RH. Depending on local,
national, or international geographic needs, the temperature and the RH settings are
fixed anywhere between 25
C/50% RH for a dry room temperature environment to a
70
C/100% RH hot-wet environment. The artificial weather conditions can also be
replicated over weeks or months of conditioning with due changes for summer, fall,
winter, and spring or a single phase conditioning that spans over the required time
can also be deployed. Needless to say, some of the artificial and accelerated
conditioning procedures provide us with the worst case influence and performance.
They are normally used by standards that are meant to test and qualify a part or a
component for performance in a rigorous environment, like the MIL-HDBK stan-
dards. Here again, not all the standards recommend conditioning up to moisture
saturation equilibrium (which means that under conditions of a set temperature and
relative humidity, the part or the component can no longer allow moisture or fluid
Water Sorption and Solvent Sorption Behavior of Epoxy/Rubber Polymer Blends 9

ingress after a given time). The swelling, change in the coefficient of thermal
expansion (CTE), and weight gain due to sorption of an epoxy-rubber blend vary
depending on a 24 h conditioning or a saturation conditioning. Here again, the time
taken for postsaturation conditioning must also be taken into account for perfor-
mance evaluation as it affects degradation.
Long-term and short-term exposures to moisture and fluids under set conditions
of temperature are recommended depending upon the application. The deficiencies
of short-term conditioning and evaluation procedures recommended for a part that
otherwise functions in a super saturated critical environment are critical and lead to a
premature and terminal behavior. For example, a polymer device meant to survive in
a human body must go through the rigors of saturation and postsaturation condi-
tioning and ensuing tests to qualify it for further use. Short-term accelerated condi-
tioning would suffice for a third or second stage booster rocket part or component
that is made of a polymer or its blend. Epoxy-rubber blends require long-term
conditioning and evaluation when used in electronic packaging applications but
need only a short-term conditioning and evaluation when used in a gasket applica-
tion for a one time operation.
To illustrate the importance of natural or long-term aging over artificial or
accelerated aging the reader is directed to Fig. 4 that explains this phenomenon
through an analogy. A chicken egg is incubated for 21 days which yields a chicken,
but cooking an omelet, boiling an egg, or toasting a bull’s eye amounts to various
schedules of accelerated aging as these three products are obtained in less than ten
minutes. Figure 4 illustrates only the irreversible component of accelerated aging.
Long-term aging and natural aging are understandably irreversible. Short-term
attacks need not be.
Table 2 provides the algorithm for moisture conditioning of the epoxy-rubber
specimens up to saturation and the method to prepare the specimens for subsequent
mechanical testing in tension, compression, flexure, impact, fatigue, and creep. The
results of the mechanical testing assist in the evaluation of degradation or improve-
ment in the respective properties after conditioning.

Theories and Laws of Sorption

The phenomenon of moisture and fluid ingress or uptake is most often governed by a
thermodynamic driving force, osmosis, reverse osmosis, or diffusion. Diffusion is
known as transport of matter through matter, assisted by concentration gradient and
temperature (Chiang et al. 1997) Thus, according to Arrhenius relationship,

D ¼ Do exp ð Ea =RTÞ (2)

Where D = Diffusivity, Do = material constant, Ea = Activation energy for diffu-

sion, R = Universal gas constant, and T = Absolute Temperature.
In polymeric materials log D versus 1/T falls on a straight line, which means that
this law is obeyed. In polymeric materials moisture has been shown to cause
10 P. Krishnan

Sunnyside up = 1 min. Hardboiled egg = 10 min. Baby chicken = 30,000 min.

at 160°C at 99°C at 37.5°C

Fig. 4 Accelerated aging through an analogy

Table 2 Algorithm for saturation conditioning and testing procedure

Procedure for environmental conditioning of test specimens

Dry specimens to equilibrium weight

(Travellers, which are the same width and thickness of the

test specimens are used to monitor moisture content)

Moisture condition specimens to percentage weight

gain to percentage humidity

Seal specimens in a MIL – B-131 metallized bag to

prevent moisture loss

Test specimens within 14 days of removal from humidity

chamber and within 8 hours of removal from bag

hygroscopic expansions or contractions analogous to thermal strains. Moisture

induced strains in isotropic materials like epoxy-rubber blends can be expressed as
a function of βc, where β is the coefficient of hygroscopic expansion and c is the
moisture concentration.
Water Sorption and Solvent Sorption Behavior of Epoxy/Rubber Polymer Blends 11

Diffusion can be termed Fickian or Non-Fickian. Fick’s first law (Fick 1855) in
one dimension states that the particle flux J (number per unit area per unit time) in a
steady state is proportional to the concentration gradient dC/dx. The proportionality
constant D is called diffusion coefficient and is written in m2/s. It is a strong function
of temperature and composition and only in some limiting cases can it be taken to be
independent of concentration.

J ¼  D: dC=dx (3)

The spatial and time distribution of concentration varies from source to source,
like a point source, semi-infinite source, line source, thin film source, or a spherical
source.
Fick’s second law (Fick 1855) describes the accrual or depletion of
concentration, C, over time when steady state conditions are not achieved and is
obtained from the spatial derivative of the flux:

@C @J 


¼  ¼ D : @ 2 C = @x2 (4)
@t @x
Fick’s laws are mass transport analogues to heat transfer laws by Fourier and the
mathematical solutions are similar. In continuum diffusion, Fick’s second law can be
used to determine the spatial concentration distribution. The value of D can vary
significantly in epoxy-rubber blends as liquid rubbers, solid rubbers, natural, and
silicone rubbers are blended with many types of epoxies. The atomistic and molec-
ular mechanisms of diffusion determine the D parameter significantly (Crank 1975).
As epoxy-rubber blends are molecular in structure, we will not digress into the
atomistic processes of diffusion that are inherent in only alloys and binary inter-
metallics.
Random walk diffusion where an atom or a molecule jumps from one location to
the other with an equal probability in the presence of a concentration gradient, obeys
Fick’s first law. The frequency with which the atom or the molecule jumps depends
on factors like the energy for migration, enthalpy of migration, temperature, and the
availability of jump sites. The availability of intermolecular distances in epoxies and
rubbers, cracks, flaws, microcracks, voids, cells, and blowholes is synonymous with
the availability of lattice defect concentration in crystalline solids. These provide the
jump sites or sites where moisture concentrates down through diffusion. Water or
solvent molecules tend to diffuse through the epoxy-rubber blends into such trap
sites and achieve saturation depending upon the driving force.
Diffusion is also a thermally activated process as described earlier in reference to
the Arrhenius relationship (Shewmon 1989). Here, the driving force for water
diffusion or solute/ion diffusion is small compared to the thermal energy kT and
can be electrical or chemical potential. It is to be emphasized that the activation
energy term, Ea, contains other energy terms such as the defect formation or
association energy in addition to the migration enthalpy caused by the thermal
activation.
12 P. Krishnan

The diffusion coefficient is often associated with impurity diffusion, chemical

diffusion, or solute diffusion, interstitial diffusion, defect diffusion, boundary diffu-
sion at the interfaces between the epoxy and the rubber phases separated due to
curing, ambipolar diffusion, and interdiffusion. The ambipolar diffusion coefficient
is restricted to ionic solids and is somewhat relevant to salt or marine water ingress
into plastics and reinforced plastics. One more quantity of interest is the mobility of
water or solvent molecules that is related to diffusivity through the Einstein-Nernst
equation.

Di ¼ kT Bi (5)

Here, Di = Diffusivity, k = Boltzmann’s constant, T = Absolute Temperature,

and -Bi is the absolute mobility that is defined as velocity/force due to the gradient in
the driving force. Though the Einstein-Nernst equation is atomistic, it can be applied
to chemical and electrical mobility correlations for solute diffusion like salt from
marine water, or solution diffusion in general, causing a change in electrical con-
ductivity provided a gradient is detected. The influence of electrochemical potentials
in conducting epoxy-rubber-complex blends is a less investigated topic and many
investigations are awaited.
Chemical diffusion is characterized by Hartley-Kirkendall effects. In case of
interdiffusion, the interdiffusion coefficient is a single coefficient D which is written
as

D ¼ XB DA þ XA DB (6)

Where XB and XA are the mole fractions of species A and B. DA is the diffusion
coefficient of B in pure A and DB, vice versa (Brophy et al. 1980). Interdiffusion in
the case of solvents, impure water, and epoxy-rubber blends is a less researched
topic. Though basic literature is available in the interdiffusion of marine water and
epoxies, much needs to be done in the area of chemical diffusion in epoxy blends.
In general, there are three types of diffusion in our system of interest. Surface
diffusion spreads through cracks, notches, and the likes; interface boundary
(IB) diffusion between two phases, viz., epoxy and rubber; and volume diffusion
of solvents, solutions, and solutes through the mass of epoxy-rubber blends. Their
relative intensities and amounts are in the following order:

Ea ðVolÞ > Ea ðIBÞ > Ea ðSurf Þ; (7a)

D ðSurf Þ > D ðIBÞ > D ðVolÞ, and (7b)

Do ðVolÞ > Do ðIBÞ > Do ðSurf Þ (7c)

As D and Do appear on either side of the Arrhenius equation, the trends in

diffusion coefficients, D, are reverse. Volume diffusion is severely affected by the
presence of blow holes, cracks, microcracks, cells, and other flaws. It is also affected
by the intermolecular distance between the epoxy molecules and rubber molecules.
Water Sorption and Solvent Sorption Behavior of Epoxy/Rubber Polymer Blends 13

In short, vacancy and interstitial diffusion are the major mechanisms in volume
diffusion of water or solvents into these blends. Diffusion can be studied at the
interfaces with the help of markers. The migration of the markers is indicative of
diffusion over a volume. An incremental addition of radio isotopes assists in the
process of diffusion measurements through detection of their migration through
diffusion.
Diffusion through a surface area is one dimensional. So, one-dimensional Fourier
and Fick’s equations can be employed. In one-dimensional diffusion, temperature
will approach equilibrium about a few tens of times faster than the moisture
concentration. This is called the Lewis number which is a function of density,
thermal conductivity, and specific heat capacity at constant pressure and diffusivity
(Soderquist 1998). The reader is referred to Fig. 2 where diffusion across a thick cast
epoxy resin plate is illustrated. It is noted that the temperature equilibrium is reached
much earlier than the moisture equilibrium. Higher ambient temperatures accelerate
the process.
Fourier’s three-dimensional transient heat conduction equation can be written as
     
@T @ @T @ @T @ @T
ρCp ¼ Kx þ Ky þ Kz : (8)
@t @x @x @y @y @z @z

where ρ is the density, Cp is the specific heat capacity at constant pressure, and K is
the thermal conductivity. T and t are temperature and time, respectively. The symbols
x, y, and z denote the spatial directions.
Fick’s three-dimensional mass transfer equation (diffusion) can be represented as
     
@C @ @C @ @C @ @C
¼ Dx þ Dy þ Dz (9)
@t @x @x @y @y @z @z

This equation represents the bulk diffusion in a solid. Bulk diffusion in epoxy-
rubber blends can be mathematically expressed by the above equation where the
moisture concentration varies spatially and along the time scale as C (x, t). It is to be
noted that time is a kinetic variable unlike temperature which is a thermodynamic
variable. Dx, Dy, and Dz are the diffusion coefficients along the x, y, and z direction,
respectively.

Diffusion Models and Mechanisms

Diffusion models are essentially twofold; single phase and two phase absorption
models are fitted to epoxies and their blends (Bonniau and Bunsell 1984). Single
phase water absorption is noticed when diamine hardeners are used to cure epoxies.
On the other hand, a two phase absorption is noticed when the same epoxy resin is
cured with a dicyandiamide hardener. For an easy understanding the single and the
two phase models are illustrated in Figs. 5 and 6.
14 P. Krishnan

I
G

N
Time in Days ---->
(%)

Fig. 5 A schematic diagram of a single phase absorption model

N
(%) Time in Days ---->

Fig. 6 A schematic diagram of a dual phase absorption model

In single phase diffusion the weight gain due to absorption can be expressed in
terms of two parameters, the diffusivity D and the weight gain at saturation Mm%. In
a two phase model, the weight gain M% as a function of time t is written in terms of
four parameters, the diffusivity D, weight gain at saturation Mm%, the probability
a of a molecule of water passing from a combined state (with the matrix) to the free
phase (not combined with the matrix) and the probability β of a molecule of water
passing from the free to the combined phase. This two phase model is also called
Langmuir model, named after the researcher who coined it first. These theories and
models are based on Fick’s laws of diffusion. However, the deviation of Langmuir
model from Fick’s laws is noticeable in many systems and more so in thin slabs and
Water Sorption and Solvent Sorption Behavior of Epoxy/Rubber Polymer Blends 15

laminates. Membranes follow the Langmuir model as two phase absorption models
are obeyed by them. Here, the combined state signifies a condition when no further
diffusion takes place. Needless to say, the concerned epoxy-rubber blends also
exhibit a single or a two phase absorption model depending upon the hardeners
and the rubber structures used.
Cross-linked epoxy resins are effective semipermeable membranes. Water mole-
cules can permeate through epoxy resin, but permeation of larger molecules or
inorganic ions is inhibited. Hence, the larger polar ions and molecules act as
inclusions and osmotic centers, providing a thermodynamic driving force for diffu-
sion of moisture into the blend. Sometimes, blisters are formed due to plasticization,
softening, and the osmotic pressure generated. Van’t Hoff’s relation gives the
osmotic pressure, π, as

π ¼ R:T:c (10)

where, R is the gas constant, T is the absolute temperature, and c is the molal
concentration of the solute (Van’t Hoff 1874).
Fluid ingress is also low into epoxy rubber blends when the salt content is high at
lower temperatures. Though insoluble solute inclusions act as osmotic pressure
centers, their concentration inhibits moisture uptake beyond a certain level. Soluble
salts have an effect on the fluid concentration in the absorbed state and are expected
to have a lesser effect. This shows why marine water attack has anomalous effects
depending on geography. This also explains why blisters form on epoxy blends with
a higher probability in hotter climates where salinity of water is low causing high
fluid ingress. Dead Sea near the Mediterranean region is a high saline sea, whereas
certain other seas are closer to fresh water ecosystems. Marine structures made of
FRPs have a higher life expectancy, provided their affinity with the solutes is
understood, ratified correctly, and the anomalous effects well quantified. Boats and
Yachts fabricated with epoxy-rubber blend composites and gel coats respond differ-
ently in different geographies, and their materials selection, maintenance, and repair
schedules have to be adaptive. The reader is now clear as to why bigger FRP ships
that are international have not found their way in to mass acceptance, as finding a
single material system, fabrication process, maintenance schedule, and repair pro-
cedure is like taking up census work in the pacific ocean. Though the experience
with smaller FRP ships like HMS Sandown and HMS Wilton have been acceptable
locally, it remains to be seen whether a truly intercontinental large ship can survive
its expected lifetime without any serious durability issues. It appears that other
candidate materials might prove superior to epoxy-rubber blends in this regard.
Fouling and bio-fouling have an impact on the water sorption of structures in
marine and fresh water ecosystems. Fouling by marine or fresh water organisms
have an adverse impact on the service life of FRP structures if their outgassing or
flatulence due to the life processes tend to degrade the FRP surfaces or coatings
through biochemical processes and open up the surfaces to severe fluid ingress. Such
a bio-hygrothermal attack severely degrades the structural integrity and the durabil-
ity of marine and fresh water structures (Pritchard 1999). Certain hydrogen and
16 P. Krishnan

hydrocarbon producing bacteria affect the adhesive bonding of FRP boat structures
making it easier for water sorption to occur between layers and cause degradation of
mechanical properties.
In essence, we have covered the isothermal and nonisothermal Fickian and
non-Fickian diffusion of moisture and fluids into polymers in general and epoxy-
rubber blends in particular. It must be emphasized that non-Fickian diffusion occurs
only due to

• The matrix containing voids

• The matrix itself exhibiting a non-Fickian two phase absorption
• Cracks, delaminations, and other damage sites in the matrix
• Moisture propagating along the weak interfaces
• Thinner Langmuir sections existing in an epoxy-rubber part
• Certain highly absorbing epoxy–natural rubber thin sections

Desorption from epoxy-rubber blends occurs due to a change in the ambience that
reverses the concentration gradient and thermal spiking in a dry ambient condition
after absorption. Reverse osmosis which aids desorption through a semi-permeable
epoxy-rubber membrane can occur due to osmotic pressures developed due to solute
and solvent ingress. Here, only pure water permeates through the micropores,
leaving the ions and heavier salts trapped in the system. Microfiltration which allows
particles of 50–100 nm size to permeate through along with water has led to later
innovations in ultrafiltration and nano-filtration methods that allow particles of only
5–10 nm and 1–2 nm, respectively, thanks to the development of nano-dispersed
epoxy-rubber blends (Thomas 2014; George et al. 2014; Jyotishkumar et al. 2011).
For water potability, RO based ultrafiltration would suffice due to the necessity to
have mineral water but the applications of nano-phase membranes in producing
nano-filtered water lie in the industrial sector where deionized water is required for
semiconductor polishing, ion exchange, and high purity applications. Desalination
plants have increasingly adopted the nano-phase technology to provide clean water
to the society. This has been achieved due to the hygrothermal studies and the
desorption studies on polymers carried out by hundreds of investigators. However,
these studies are on other polymers and not on epoxy-rubber blends. The author
looks forward to the use of epoxy-rubber wastes in landfills that lead to purification
of water through permeation and collection as a first step in producing cheap and safe
potable water that also addresses the environmental issues.
Viscoelasticity models for epoxy-rubber systems after hygrothermal conditioning
are not too different from the nonlinear 3 parameter Martinus Burger model and the
5 parameter friction model of Mat Berg that also is nonlinear. The linear 3 parameter
Zener model is rarely acceptable to epoxies here as rubber additions and further
plasticization due to hygrothermal attack up to saturation renders them nonlinear.
There is no literature available on the influence of hygrothermal conditioning on
WLF equations, relaxation times, and retardation times of epoxy-rubber blends.
A Fickian model for diffusion of moisture in permeable fiber polymer composites
is discussed by Rao et al. (1984). Springer has contributed significantly to the
Water Sorption and Solvent Sorption Behavior of Epoxy/Rubber Polymer Blends 17

understanding of epoxy based composites and their environmental degradation

(Springer 1980, 1984, 1988). However, moisture or fluid ingress in epoxy-rubber
blends and their composites is a rarely researched topic as seen from the publications
that have been documented. Some of the interesting investigations are available as
publications with a limited understanding.

Performance and Function After Hygrothermal Attack

A recent investigation describes the effect of hot-wet conditioning and low temper-
atures on reliability, esp. fatigue of epoxy based composites (Bhanage and
Padmanabhan 2016). Another investigation details the effect of hygrothermal con-
ditioning on the mechanical properties of epoxy based composite laminates. Diffu-
sion has been dealt with in greater details (Deepa et al. 2016). Clint and Wicks have
discussed the adhesion of contaminants under water on polymer surfaces that are
driven by the surface energies (Clint and Wicks 2001). This paper is important from
the marine standpoint as it describes the ease at which contamination occurs on
epoxy surfaces. Anticorrosive siliconized epoxy coatings have been developed by a
team (Gupta and Bajpai 2011). Preparation of blends of epoxidized novolac resin
and carboxylic terminated polybutadiene (CTPB) liquid rubber and evaluation of
their physico-chemical characteristics has been discussed in detail (Tiwari et al.
2010). Perhaps, some of the solitary but interesting investigations on the effect of
moisture on the properties of epoxy-rubber blends come from two investigators (Lin
and Yeh 2002). These moisture absorbing materials act as sensors and switches in
electrical and electronic applications as conductivity changes due to moisture
absorption can be measured (Adhikari and Majumdar 2004). This exhaustive review
article details the use of moisture absorbing polymers as moisture sensors with
excellent applications. Rare cases of matrix stiffening due to moisture ingress and
saturation conditioning are also reported. The changes brought forth by varying
humidity, temperature, or thickness of an epoxy based fiber composite is well
illustrated in Figs. 7, 8, and 9. It is clear from the illustrations that both Fickian
and non-Fickian diffusion and absorption behavior are exhibited by these compos-
ites as humidity, temperature, or thickness are varied over a time period.
Thus, it can also be argued that Fickian or non-Fickian diffusion is also extrinsic
as well as geometry oriented and need not depend only on the structure of epoxies,
epoxy blends, or their composites. The three figures have been included as a case
study to emphasize the importance of the time factor as what would look like
non-Fickian could become Fickian due to a dwelling or leveling effect at longer
time periods approximating with that of the single phase models.
Or it would simply stay non-Fickian and obey a double phase absorption model
over a set period of time. This brings out the conditional and vital importance of
long-term aging and natural long-term aging of these materials and the evaluation for
durability thereafter. The conditioning and evaluation studies could also be simulta-
neous, if long term. Water and fluid uptake studies should be commensurate with the
real time and real environment applications. To reinstate the facts, submersible FRP
18 P. Krishnan

Fig. 7 Moisture absorption

of a typical HTS carbon/
epoxy laminate at different
RH values

Fig. 8 Moisture absorption

of the same laminate at 1.6 Moisture Absorption
different temperatures 1.4
Moisture content (%)

1.2
1
0.8 75 deg F
0.6
120 deg F
0.4
150 deg F
0.2
180 deg
0
0 2 4 6 8 10
Time (days)

storage tanks in petrol stations are to be evaluated for their long-term durability
through rigorous conditioning and evaluation tests whereas that of one stop pro-
cesses in external medical devices be taken through an accelerated process for
qualification for the purpose, as the same material/device cannot be used again due
to concerns for hygiene. It is important to add that epoxy-rubber blends are never
used for internal bio-medical applications due to toxicity and lack of
bio-compatibility and their long-term conditioning do not find any applications here.
Figure 10 illustrates the shrinking operational limit of an epoxy-blend composite
due to wet conditioning. Increasing moisture content reduces the operational limits,
the thermal ceiling or the MOT (Maximum Operating Temperature), and the failure
strain of the composite. Though schematic, the figure is an indication of the
degradation in mechanical properties over time when the material is exposed to
hygrothermal attack.
Water Sorption and Solvent Sorption Behavior of Epoxy/Rubber Polymer Blends 19

Fig. 9 Moisture absorption

of the same composite at
different thicknesses

Fig. 10 A schematic illustration of dry and wet operational limits

Summary and Conclusions

The water, solute, and solvent sorption behavior of epoxy/rubber polymer blends of
various structures are discussed in this chapter in a detailed but lucid manner keeping
the graduate student in mind. The moisture affinities of epoxies, rubbers, and their
20 P. Krishnan

blends are quantified to enable materials selection. The sorption phenomena are
explained in these blends with respect to the surrounding temperature, relative
humidity, moisture concentration profiles based on parameters like diffusion, part
and laminate thickness, weight gain due to absorption over time, and saturation
equilibration. The statistical design criteria to be adopted after hygrothermal condi-
tioning is listed. Short term and long-term conditioning, natural and artificial aging,
the influence of structure, and the observed mechanisms of sorption have been
illustrated. Here again, distinction is made between the sorption characteristics of
solid rubber/epoxy and liquid rubber/epoxy blends. A summary of the types of
diffusion encountered is clearly spelt out with mathematical foundations. A reason-
able correlation is attempted through Fickian and non-Fickian absorption models for
epoxies, rubbers, their blends, and the observed properties that lead to novel
applications. A brief account of the viscoelastic models for the saturation condi-
tioned epoxy-rubber blends is provided. The observed changes in the physical,
chemical, mechanical, and electrical properties of the blends are documented. The
hygrothermal performances of fiber composites fabricated with epoxy/rubber blends
as the matrix materials are also discussed and presented along with their applica-
tions. The present state of available literature, implications from availability, and
futuristic directions to take are detailed as suggestions for further work at the end.

Implications and Suggestions for Further Work

After a careful perusal and documentation of the available literature, the following
topics are suggested as potential themes that researchers could take up as a disser-
tation, thesis, or funded project work. It is a matter of concern that the ratio of
investigations that deal with the dry properties to those which deal with the wet
properties for the same systems is alarmingly high. It is imperative that once epoxy-
rubber blends are used, their moisture susceptibility and the long-term durability
assume significance. Unfortunately, this knowledge gap has assumed gross pro-
portions and the author considers it his prime duty to bring the dearth of literature
on this front to the attention of potential case workers and suggest a few problems
that are sensitive, considered mandatory, and would lead to further development.
Some of the interesting problems could be:

1. Synthesis and development of high temperature epoxy systems with hydropho-

bic silicone and RTV rubber blends through microstructural modification for
extra toughness, strength, and durability.
2. Intelligent use of hygrothermal attack that can be used to modify the chemistry
and curing of epoxy systems that would cure in the presence of moisture at
elevated temperatures.
3. Nano phase rubber-epoxy networks could be developed for improved
hygrothermal resistance.
4. Advanced self-healing interpenetrating polymer networks (IPNs) of rubbers and
epoxies that find wide structural applications could be developed.
Water Sorption and Solvent Sorption Behavior of Epoxy/Rubber Polymer Blends 21

5. Epoxy-rubber systems that find applications as moisture switches and sensors in

electronics and electrical systems could be developed.
6. High temperature epoxy-rubber systems with low moisture absorption can be
developed for high voltage insulation applications.
7. Electrochemical aspects of diffusion and mobility that could be evaluated for
conducting epoxy-rubber complexes.
8. Moisture resistant high temperature epoxy-rubber blends are potential candi-
dates as sealants, gaskets, O-rings, and pressure sensitive adhesives. These can
be synthesized.
9. Chemical diffusion between rigid polymers and solvents/solution is a less
investigated topic. This can be taken up.
10. Fickian and non-Fickian diffusion in epoxy-rubber adhesives and film adhesives
is structure and dimension dependent. An understanding of the models and the
mechanisms is required.
11. Nanoblend epoxy-rubber and nano-porous membranes can be developed for
reverse osmosis and solvent purification.
12. Epoxy-rubber wastes can be used in landfill dumps for ground water purification
and use.
13. Synthesis and characterization of other hydrophobic rubbers and blending with
epoxies that find moisture resistant applications.
14. Studying the influence of hygrothermal conditioning on time-temperature super-
positions, WLF equations, relaxation times, and retardation times of epoxy-
rubber blends.

The list is unending and exhaustive and the author is hopeful that many able
investigators would fill the knowledge gap in future.

References
Adamson MJ (1983) A conceptual model of the thermal spike mechanism in graphite – epoxy
laminates. Long term behaviour of composites, ASTM STP 813, ASTM, Philadelphia, p 179
Adhikari B, Majumdar S (2004) Polymers in sensor applications. Prog Polym Sci 29:699–766
ASTM D 5229/D 5229M (1998) Moisture absorption properties and equilibrium conditioning of
polymer matrix composite materials
ASTM D 570 (1995) STP for water absorption of plastics
ASTM D 618 (1996) SP for conditioning plastics for testing
ASTM D 696 (1991) STP for coefficient of linear thermal expansion of plastics between 30
C
and 30
C
ASTM D 756 (1993) SP for determination of weight and shape changes of plastics under
accelerated service conditions
Bhanage A, Padmanabhan K (2016) Fatigue and crashworthiness of automobile materials after
DBTT and hygrothermal conditioning. In: Proceedings of the ISET 2016 ICDMM, 19–20 Feb,
Pune
Billmeyer FW (2015) A text book of polymer science. Wiley, New York
Blow CM, Hepburn C (1982) Rubber technology and manufacture, 2nd edn. Butterworth Scientific,
London
22 P. Krishnan

Bonniau P, Bunsell AR (1984) A comparative study of water absorption theories applied to glass
epoxy composites in Springer GS, Chapter 18. In: Environmental effects on composite mate-
rials, vol 2. Technomic Publishers, Lancaster, Pennsylvania
Brophy JH, Rose RM, Wulff J (1980) Thermodynamics of structure, vol 2, Structure and properties
of materials. Wiley Eastern Publications, New York
Chamis CC, Sinclair JH (1982) Durability/life of fibre composites in hygrothermomechanical
environments, ASTM STP 787, ASTM, Philadelphia, PA, pp 498–512
Chiang YM, Birnie DP III, Kingery WD (1997) Physical ceramics. Wiley, New York
Ciba-Geigy Information sheet No: FTA 46d, May (1983) pp 1–15
Ciba-Geigy Information sheet No: FTA 49e August (1984). Duxford, Cambridge
Clint JH, Wicks AC (2001) Adhesion under water: surface energy considerations. Int J Adhes
Adhes 21:267–273
Crank J (1975) Mathematics of diffusion. Oxford University Press, New York
Deepa A, Padmanabhan K, Raghunadh G (2016) Effect of hygrothermal loading on laminate
composites. In: Proceedings of the 2nd international conference on Design, analysis,
manufacturing and simulation, (ICDAMS-2016), 7–8 Apr, Chennai
Fick A (1855a) Ann. der Physik (in German) 94:59. doi:10.1002/andp.18551700105
Fick A (1855a) Diffusion in solids. Philos Mag 10:30
Fick A (1855c) On liquid diffusion. Poggendorffs Ann 94:59. Reprinted in J Membr Sci 100:33–38
Gabriel OS, Advani SG (2003) Core-shell rubber/epoxy blends, rheology. In: Advanced polymeric
materials, Structure property relationships. CRC Press, Boca Raton
Garg AC, Mai YW (1988) Failure mechanisms in toughened epoxy resins. A review. Compos Sci
Technol 31:179–223
George SM, Puglia D, Kenny JM, Parameswaranpillai J, Thomas S (2014) Reaction-induced phase
separation and thermomechanical properties in epoxidized styrene-block-butadiene-block-sty-
rene triblock copolymer modified epoxy/DDM system. Ind Eng Chem Res 53:6941–6950
Gibson RF (1994) Principles of composite material mechanics. McGraw Hill International Editions,
New York
Gupta P, Bajpai M (2011) Development of siliconized epoxy resins and their application as
anticorrosive coatings. Adv Chem Eng Sci 1:133–139
Jyotishkumar P, Pionteck J, Haßler R, George SM, Cvelbar U, Thomas S (2011) Studies on stress
relaxation and thermomechanical properties of poly(acrylonitrile-butadiene-styrene) modified
epoxy–amine systems. Ind Eng Chem Res 50:4432
Lee SM (1989) Reference book for composites technology, vol 2. Technomic, Lancaster, p 61
Lee HL, Neville K (1967) Handbook of epoxy resins. McGraw-Hill, University of Michigan,
New York
Lin KF, Yeh RJ (2002) Moisture absorption behavior of rubber-modified epoxy resins. J Appl
Polym Sci 86:3718–3724
Mallick PK (1994) Fibre reinforced composites, 2nd edn. Marcel and Dekker, New York
MILHDBK Standards (2002) MIL-HDBK-17-1, Philadelphia, PA, Version: F, Date: Jun-17,
(Vol 1–5)
Padmanabhan K (2006) ‘The need to revise standards on dental restoratives’. A commentary. Curr
Sci 91(4):418
Padmanabhan K (2009) Comments on standards on restoratives. Indian J Dent Res 20(4):514
Padmanabhan K (2015) 3rd Interim report, Project No: 1650, ARDB Structures Panel
Padmanabhan K (2016) A multiphysics based finite element approach to evaluate the reliability of
IC packages, Chapter 2. In: Handbook of Research on Advanced computational techniques for
simulation based Engineering, IGI Global
Parida BK, Rao RMVGK, Padmanabhan K (1996) Airworthiness considerations in certification of
Frp composite materials for civil aircraft development. In: Proceedings of third jointnational
aerospace laboratories Chinese Aircraft Establishment Work Shop on composites, 22–24 Apr,
Bangalore, p 9
Water Sorption and Solvent Sorption Behavior of Epoxy/Rubber Polymer Blends 23

Powers DA (2009) Interaction of water with epoxy, SANDIA REPORT, SAND2009-4405, Unlim-
ited Release
Pritchard G (1999) Reinforced plastics durability. CRC Press/Woodhead Publishing, Cambridge,
UK
Rao RMVGK, Chanda M, Balasubramanian N (1984) A fickian diffusion model for permeable fibre
polymer composites, Chapter 16. In: Springer GS (ed) Environmental effects on composite
materials, vol 2. Technomic Publishing, Westport
Shewmon P (1989) Diffusion in solids. TMS, Warrendale
Soderquist J (1998) Design/certification considerations in composite aircraft structure. Federal
Aviation Administration, Springfield, Virginia, Apr 1998
Springer GS (1980) Environmental effects on composite materials, vol 1. Technomic Publishing,
Westport
Springer GS (1984) Environmental effects on composite materials, vol 2. Technomic Publishing,
Westport
Springer GS (1988) Environmental effects on composite materials, vol 3. Technomic Publishing,
Westport
Thomas S (2014) Rheology of rubber toughened structural epoxy resin systems. Wiley-VCH,
New York
Tiwari AK, Kumar H, Bajpai R, Tripathi SK (2010) Preparation of blends of epoxidised novolac
resin and carboxylic terminated polybutadiene (CTPB) liquid rubber and evaluation of their
physico-chemical characteristics. J Chem Pharm Res 2(3):172–178
Van Hoff JH (1874) Sur les formules de structure dans l’espace. Arch Neerl Sci Exactes Nat
9:445–454