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INTRODUCTION
Abstract
In this chapter we present an overview on polymer blends,
their classification, thermoplastic elastomers, thermodynamics of
miscibility, different compatibilisation strategies including
dynamic vulcanization, theories of compatibilisation and phase
morphology development. Special attention is given to review the
recent studies and advances related to the system under
consideration. Finally, the scope of the present area of research and
the precise objective of the present topic of research are described.
Chapter 1
In the last few decades the continuous need for materials of high
technological properties has stimulated scientists to develop new classes of
polymers with special properties, which can able to serve in applications
where the usual materials fail. One of the most exciting and rapidly
expanding branches of materials science is in the area of polymers.
Many new multi component polymeric materials have been
developed during the past few decades. The large number of scientific
papers, industrial patents, scientific meetings and exhibitions devoted to
this class of materials is sufficient to witness the strategic importance of
field.
There are a variety of polymers available in the market. However, a
single polymer often cannot achieve the desired properties for industrial
applications. Developing a new polymer with a new chemical structure that
fits the needs of the market is very difficult and costly process. So blending
of polymers is an indispensable for developing new polymeric materials.
Hence new marketable polymer entities are introduced rapidly.
1.1 Polymer Blends
Blending is an art of mixing two or more polymers for getting a
unique property. Polymer blends have played a significant role in the last
few decades in revolutionizing polymer technology, leading to important
and useful applications. The term polymer blend may be defined as a
combination of two or more structurally different polymers or copolymers
giving rise to materials with a range of properties, not delivered by any of
the constituents. Thus, the reason for using blends include the attainment of
specific article performance, by improving the technical properties of the
original polymers, or by adjusting the processing characteristics and
reducing the cost [1-5]. The possibilities of blending of the major polymers
Introduction
are infinite, and the market place will dictate the tailoring of the blends.
Most pairs of polymers are thermodynamically immiscible, but some
polymer blends are compatible and exhibit excellent physical properties
that offer advantages over either of the individual polymers. Sometimes a
third component is added as a compatibiliser, which allows the blending of
the two immiscible polymers.
Polymer blends are made by compounding on mill rolls, in
extruders or in banbury mixtures. Almost all are heterogeneous and consist
of a polymer matrix in which another polymer is embedded. Compatibility
plays an important part in design and optimization of polymer blends.
1.2 Methods of Blending
There are several methods appeared in the literature to make
polymer blends.
1.2.1 Melt blending
Blends can be prepared by melt mixing the ingredients in an internal
mixture. Melt blending avoids contamination and presence of solvent. The
primary disadvantage of melt mixing is the possibility for degradation and
high cost of equipments.
1.2.2 Solution blending
Casting blend from a common solvent is the simplest mixing
method available and is widely practiced. In this method component
polymers are dissolved in a common solvent. In this case there is no chance
of degradation. The main limitation of this method is the incompatible
nature of polymers in many of the commonly used solvents. Residual
solvents can influence the analysis results and is very difficult to make
thick films using this method. Moreover, the waste solvents can cause
environmental problems.
Chapter 1
Introduction
Chapter 1
Thermoplastic Elastomers
Elastomers are really wonderful class of polymers. Crosslinking
makes this all possible. But crosslinked polymers can't be recycled very
easily. So in the interests of keeping the earth from becoming a giant
landfill, researchers have come up with a new approach, the thermoplastic
elastomer. The idea behind thermoplastic elastomers is the notion of a
reversible crosslink.
A thermoplastic elastomer (TPE) is a rubbery material with
properties and functional performance similar to those of a conventional
vulcanized rubber; still it can be processed in a molten state as a
thermoplastic polymer. These are relatively new class of materials, which
Introduction
Chapter 1
and ionic bonding and other dispersion forces. But in both ionomers and
block copolymers, forces are much weaker than those of the covalent bonds
present in the "crosslinked" polymer chains.
The beauty of using noncovalent interactions to form crosslinks in
TPEs is that when the material is heated, the crosslinks are broken at a
given temperature, which will result in the separation of polymer chains. So
right amount of heat separates the chains from each other. This allows the
material to be processed, and most importantly be recycled. When it is
cooled, the cross links will be reformed.
1.4.1 Advantages of TPEs
(i)
(ii)
(iii) Processing times for TPEs are shorter since the long cycle time
required for vulcanization is eliminated. Cycle time is typically
seconds instead of the minutes required for thermoset rubbers. This
enhances productivity and reduces costs.
(iv) Being thermoplastic, TPE scrap generated during processing can be
recycled without any loss in functional properties. In contrast,
thermoset elastomers are not recyclable.
Introduction
(v)
(ii)
(ii)
Chapter 1
10
Ease of preparation
(ii)
(iii)
(iv)
Introduction
11
A
B
C
Volume fraction
Figure 1.1: Schematic diagram for the variation of free energy change
with composition in binary polymer mixture.
Chapter 1
12
2
wIi T , P
U A
UB
RT
2B ! 0
I A M A IB M B
(1.1)
(1.2)
Introduction
13
M i ln M i
i 1
Ni
j 2
j 1
M M
i
F ij
..(1.3)
i 1
F ij
Vo
G i G j )
RT
(V0= volume)
..(1.4)
Chapter 1
14
Introduction
15
Chapter 1
16
with poor structural integrity and heat stability and their performance will be
irreproducible. As mentioned earlier, the high interfacial tension is derived
from the unfavourable interfacial interactions between the individual phase
leads to a large interfacial tension in the melt, which make it difficult to
disperse the components finely enough during mixing and drives phase
rearrangements (coalescence). A poor interfacial adhesion results in an
immature stress transfer, which cannot prevent cracks initiation at the
interface from growing until catastrophic failure occurs. Both theories and
experiments support the role of compatibiliser in multiphase polymer
systems.
1.6.1 Strategies for compatibilisation
whereas
the
latter
procedure
is
called
reactive
Introduction
17
terephthalate/ethylene
propylene
diene
terpolymer
Chapter 1
18
Physical
compatibilisation
is
the
classical
approach
to
Introduction
19
(a)
(b)
Chapter 1
20
Introduction
Blending conditions
21
Reactive compatibilisation is one of the most important costeffective mixing technique by which one can generate new multiphase
polymeric systems with stable and controlled morphologies. The reactive
compatibilisation technique has several advantages over physical
compatibilisation. During reactive blending the interfacial chemical
reaction gives raise to in-situ formed copolymers, which suppress the
coalescences and reduce the interfacial tension. As a result of this, a stable
and a fine morphology is obtained with enhanced interfacial adhesion
between the phases. Additionally most of these reactions are very fast and,
they can be performed with in the time scale of an industrial extruder.
The reactive polymers may be obtained by polymerization through
terminal, backbone and side chain groups by copolymerisation of
monomers containing the desired reactive groups, and by chemical
modification of pre-formed polymers using free radical grafting,
Chapter 1
22
substitution, terminal modification etc. There are three main scenarios for
reactive compatibilisation of two immiscible polymers.
1. The base polymer components are mutually reactive. In this case
reactive compatibilisation is straightforward. The reaction between
them at the interfaces will lead to the formation of a copolymer.
2. One polymer bears potentially reactive groups and other is
chemically inert with respect to them. Reactively compatibilising
them requires that the non-reactive polymer be functionalized with
functional groups that can react with the reactive one. An alternative
is to introduce a reactive polymer that is miscible with the nonreactive polymer and can react the reactive one.
3. Neither of the base polymers contain reactive group. In such cases,
different compatibilisation methods can be used. The first one is to
add two reactive polymers that are mutually reactive and miscible
with component polymers. The second one is to fuctionalize
component polymers with different functional groups, which are
mutually reactive.
1.6.1.2.1 Advantages of reactive compatibilisation
Introduction
23
Chapter 1
24
Maleic anhydride
Carboxylic acids
Hydroxyl groups
Heterocyclic groups
Others
Some of the important reactions involved in reactive compatibilisation
Introduction
25
Reactive Group
Co-reactive group
Amidation
Carboxylic acid
Amine
Imidation
Anhydride
Amine
Esterification
Hydroxyl
Concerted addition
Maleate and MA
Double bond
Urea formation
Carbodiimide
Carboxylic acid
Urethane formation
Isocyanate
Hydroxyl
Substitution
Amine
Hydroxyl, halide
Ester interchange
Ester
Ester
Transesterification
Ester
Hydroxyl/Phenol
Amide-ester
exchange
Amide
Ester
Aminolysis
Ester
Amine
Amide interchange
Amide
Amide
Acidolysis
Ester
Carboxylic acid
Ring-opening
reaction
Epoxide
Ring opening
reaction
Oxazoline
Remarks
Addition/
Substitution
Addition/
Substitution
Interchange
reaction
Ring-opening
reaction
Lactam
Ionic bonding
Acid
Ionic bonding
Ionomer
Ionomer
Ring-opening
reaction
Amine
Ionic bonding
(i)
Amine-anhydride reaction
Chapter 1
26
Literature survey also reveals that the imidisation reaction has been
extensively used for the compatibilisation of polymer blends recently [125138].
(ii)
groups. Amidation is less efficient and less frequently used when compared
to imidation reaction. Primary amines were found to be more reactive than
other amines towards the carboxylic acid attached to the polymers. This
method has been widely used for several researchers [139-143]. This types
of compatibilisation have been mostly used for improving the impact
strength, tensile strength, permeability, compatibility, morphology and
Introduction
27
Chapter 1
28
O
H3C
C O
CH2
O
H3C
CH CH2 + HO C
O
C O CH2
CH CH2
O C
OH
oxazoline)
(RPS)
with
copolymerized
oxazoline
Introduction
29
O
R1
R2
H
N
R2
R1
R1
NH2
R2
COOH
R1
N
H
R2
O
Epoxy
HOOC PBT OH
PBT
O
a.)
b.) O
PBT OH
OH
R
PBT COOH
OH
Figure 1.10(b): Scheme of reaction between epoxide (a) with COOH (b)
with -OH groups of PBT
(S.C. Jana, N. Patel, D.
Dharaiya, Polymer, 42, 8681, 2001.) [Ref.158]
(vi)
Transreactions
Chapter 1
30
P1-O-CO-P2+OH-P3
Transesterification
P1-O-CO-P2+P3CO-O-P4
Aminolysis
P1-NH-CO-P2 + H2N P3
Transimidation
P1-NH-CO-P2 + P3 CO-NH-P4
Acidolysis
P1-O-CO-P2+ HOOC-P3
Ester-amide
P1-NH-CO-P2 + P3 CO-O-P4
interchange
P2CO-O-P4
(vii)
P1-OH + P3-O-CO-P2
P1-O-CO-P3+P2-CO-O-P4
P1NH2+P3NH-CO-P2
P1-NH-CO-P3 + P2 CO-NHP4
P1-O-CO-P3+ HOOC-P2
P1-NH-CO-P3 +
Ionic interactions
The reactive group content will affect the extent of the interfacial
chemical reaction and the molecular architecture of the in-situ formed
compatibiliser. By increasing the amount of the reactive groups on a
reactive polymer from one to multiple groups, the structure of the graft
changes from a single to a multi-graft comb like structure. At the same
time, the extent of interfacial reaction which is a function of the content of
the reactive groups available will affect the stability of the formed
Introduction
31
tension
and
increased
interfacial
stabilization.
If
the
Chapter 1
32
At the same time a very low affinity of the compatibiliser for one of the
phases can cause its migration to the other phase.
Majumdar et al. [169] studied the use of imidized acrylic polymer
as a compatibiliser precursor in nylon6/SAN system. One can anticipate at
least three different locations of the block or graft copolymer formed in
blends as illustrated in Fig.1.11. If the imidised acrylic polymer is fully
miscible with the SAN phase, one may expect it to reside primarily within
the SAN phase, with its functional group (A) forming chemical linkages to
nylon6 chains at the interface as shown in Fig.1.11a. This situation is
expected to provide the most efficient reduction in the SAN domains
particle size through a decreased interfacial tension and increased steric
stabilization. Fig.1.11b illustrates the situation in which the functionalized
compatibilisers reside at the SAN interface because it has some
thermodynamic affinity for this phase, but not enough to be miscible with
it. The third situation, shown in Fig.1.11c, arises when the compatibiliser is
even less attracted to the SAN phase and, hence, resides in the polyamide
phase away from the interface. This situation will not result in any
strengthening of the polyamide-SAN interface; however, the formation of
these highly grafted micellar aggregates will increase the viscosity of the
polyamide matrix which in turn, leads to a change in the morphology of the
blend.
Introduction
33
Chapter 1
34
upon
annealing
while
the
reactively
compatibilised
Introduction
35
Chapter 1
36
'J
d ) c 1 2 F 1 Z c 1 Z c exp Z c F 2
.(1.5)
where d is the width at half height of the copolymer profile reduced by the
Kuhn statistical segment length, ) c the bulk copolymer volume fraction of
the copolymer in the system, Z c the degree of polymerisation of the
copolymer and F the Flory-Huggins interaction parameter between A and B
segments.
1.7.2 Leiblers theory
Introduction
'J
37
kT a 2 3 4
13
2 5 3
6 a Z
CA
Z A 2 3 Z CB Z B 2 3
(1.6)
J0
48 P 3 2 F N 1 2
(1.7)
ln I f F N
(1.8)
I0
Im Id exp ^F N A N B `
(1.9)
Chapter 1
38
3 2
1 2
N P
(1.10)
'J
1 Z c exp Z c F1 2 F 2
for : F1 { F BY
F AX
F XY
F AB and F 2 { F AY
.(1.11)
F BX ! F1
Introduction
39
Q 12
IE
N'g I 1 2 dI
2
N { w 2 g wI w 2I w 2 g w I
.(1.12)
(1.13)
J 12
^IJ
CMC
ImeanJ 0 I Imean `
where J CMC { J 12 Ic
.(1.14)
dC
K J J s
..(1.15)
where K is the rate constant for the change in interfacial tension with
concentration of the compatibiliser, J the interfacial tension at a given
Chapter 1
40
R Rs
(R 0 R s )e kC
...(1.16)
where R0, R and Rs are the average radius of dispersed particles without
compatibiliser, at a given compatibiliser concentration and compatibiliser
concentration at CMC respectively. A plot of ln R Rs versus C can be
used to obtain k from the slope.
1.7.7 Paul and Newmans theory
According to Paul and Newman [194] the interfacial area per unit
volume occupied by each compatibiliser molecule is given by the expression:
6
3I M
RNW
..(1.17)
Introduction
41
S R2 M A 3 1
k
NRg2 4S R3 UWA
3kM A
4 Rg2 RN UWA
..(1.18)
Dynamic Vulcanization
Chapter 1
42
Introduction
43
Chapter 1
44
Figure 1.13:
1.9
Introduction
45
When two immiscible polymers are mixed, the size, shape and
relative distribution of one phase into the other depend on material
parameters such as blend composition, viscosity ratio, elasticity ratio and
interfacial tension as well as processing conditions like temperature, time,
intensity and type of mixing and nature of flow. Therefore the greatest
challenge in the field of multiphase polymer blend research is the
restructuring of polymers via judicious control of the melt flow during
processing and the interfacial interactions. The mechanism of development
of morphology from pellet sized or powder sized particles in polymer
blends are directly derived from the complex interplay of material
parameters and processing conditions. As a result of this, for a given blend,
different types of morphologies are possible. However, from the point of
view of the performance, they can be categorized into four basic
morphology types (Fig.1.14).
x
Matrix-fibre structures
Lamellar structures
Co-continuous structures
Other important types of morphologies are fibrillar, core shell,
46
Chapter 1
Introduction
47
OK
K d T , J
K c T , J
.(1.19)
Chapter 1
48
where d is the viscosity of the dispersed phase and c is the viscosity of the
matrix phase.
Elasticity ratio of the components
OT
T d T , J
T c T , J
.(1.20)
We
K.J .R
J dc
.(1.21)
J .t v
K.J .R / J dc
t v .J dc
K .R
.(1.22)
6.J .M d2
S 2 .R 3
.(1.23)
Introduction
49
Morphology development
There has been a flurry of activity in the area of polymer blend
morphology development over the last few years. Fig.1.19 shows the
important mechanisms during blending of immiscible polymers.
Chapter 1
50
Introduction
51
The figure also shows the effect of stabilization on final drop size.
Once domains reach the micron size scale, they may be stretched into
filaments and are then broken into droplets. At this size scale, interfacial
forces become important and pull in the edges of the stretched domains,
giving cylindrical or filament type morphology. The stretching and
breaking up of filaments is due to the combined effect of high shear zones
and low shear zones in the mixture [265]. The domains are stretched in the
high shear zones and then relax and break up in the low shear zones via
Rayleigh type instabilities. It may be possible to form drops directly from
sheets but only at very low shear rates. Much polymer blending work
reports filaments even at the end of the mixing process [266,260], and this
may be a result of a high shear zone at the end of the process [265]. Break
up phenomena in polymer blends are non-Newtonian in nature
[243,249,260,261,267-270].
Fig.1.21 shows an example of an investigation of the dispersion
behaviour of real polymer blends. Favis and Chalifoux [271] investigated
blends of polypropylene (PP) and polycarbonate (PC) with respect to the
correlation between the average droplet size and the viscosity ratio. The
viscosity ratio is found to have a marked effect on the morphology of the
dispersed phase.
52
Chapter 1
Introduction
53
Chapter 1
54
polymer
melting
temperature
[250-257],
indicating
that
the
Introduction
55
Figure 1.24: Phase inversion mechanism (a) sheets are pulled off the
softening pellets near the softening transition of the major
phase. (b) The sheets from lamellar domains inside the
minor phase(c) break up into irregular pieces (the minor
phase is also breaking up at this point) until (d) phase
inversion occurs during processing through coalescence of
the major phase domains. (U. Sundararaj, C.W. Macosko,
C.K. Shih, Polym. Eng. Sci. 36, 1769, 1996) [Ref: 262]
Various authors found that phase inversion was dependent on the
ratio of the blend composition and the ratio of the viscosities [282,283]:
M1 K 2
.
M 2 K1
(1.24)
Chapter 1
56
The above equation implies that only the viscosity ratio of the
components determines the volume fraction at which phase inversion takes
place.
Fig. 1.25 shows schematically the progress of the zone of continuity
in a theoretical polymer system.
Introduction
57
Chapter 1
58
Introduction
59
Chapter 1
60
the
dispersed
phase
concentration
is
increased
in
Introduction
61
Chapter 1
62
K mJ R
*
..(1.25)
where m is the matrix viscosity, is the shear rate, R is the drop radius and
is the interfacial tension. When the viscous forces are much greater than
the interfacial forces, drop break up is expected. The capillary number is
Introduction
63
more appropriate for polymer blends since, due to the high polymer
viscosity, the flows are typically laminar flows, and viscous forces
dominate. Wu defined a critical capillary number (Weber number) for
viscosity ratio above which drop breaks up occurred.
2C a
4K r
r0.84
(1.26)
The Weber number is widely used in emulsions since inertial forces are
important. Favis and Chalifoux [293] showed similar trends in their work.
1.9.2.4.1 Effect of composition
Much of the early research on polymer blends concentrated on the
effect on the composition since by changing the composition, one could
easily alter final blend properties. It was found that increasing the
composition typically increased particle size up to the cocontinuous
morphology region [299,293,313,322,324]. There have been few
exceptions to this general observation at higher concentrations [325]
because of the influence of the dispersed phase viscosity on dispersed phase
domain deformation. Sundararaj and Macosko [313] showed that the
particle size increased with concentration of dispersed phase due to
coalescence in uncompatibilised blends. At low concentrations, the particle
reached a limiting size. The limiting size should correspond to the dilute
solution limit. It was found that the drop size was greater than that
predicted by Taylors limit [326,327], but lower than that predicted by
Wus correlations. The lower drop size observed at low concentration is
lower than that obtained by Wu because coalescence was present in Wus
data. The discrepancy with the Taylor limit was explained to polymer
elasticity for the drop.
Chapter 1
64
1.2K r
r0.45
(1.27)
In addition, they found that at low viscosity ratios Taylors limit is valid,
but at higher viscosity ratios, the drop size is greater than Taylors limit and
lower than Wus correlation. Taylor predicts no break up for viscosity
ratios above 4, and yet break up is seen in many polymer blends with much
higher viscosity ratios [292,293,313,328]. Recent work using model
mixtures has shown that polymer drops can break up in simple shear at
viscosity ratios above 4 [251,254,256,257,259,329,330,]. It is now clear
that polymer drops behave very differently from Newtonian drops and that
Ca or r alone may not be sufficient to describe the break up.
1.9.2.4.2 Effect of shear rate
The customary expectation is that the dispersed phase domain size will
decrease with increased shear rate. Even when considering the shear thinning
nature of polymer viscosity, the shear stress continues to increase with
increasing shear rate so drop size should decrease at higher shear rate.
However, most works studying the effect of the shear rate on morphology in
polymer blends do not show this trend. As the shear rate was increased Favis
[268] found a modest decrease initially and then a levelling off in the particle
size. White and coworkers found that changing the shear stress did affect the
particle size [331] while Walczak found that changing the shear stress by a
factor of three had little effect on structure [332]. During mixing, Plochocki et
al. [291] observed that the drop size decreased initially as the shear rate was
increased, and then the drop size actually increases at higher shear rates. The
authors explained that an optimum energy input or specific energy
consumption (SEC) gave a minimum drop size. Ghodgaokar and Sundararaj
Introduction
65
[270] also observed a minimum drop size at an intermediate shear rate and use
a force balance to predict this behaviour.
1.9.2.4.3
Effect of temperature
Chapter 1
66
capability for mixing and do not have the folding reorientation. A mechanism
that has been found to be important for blending [265,338,339]. For batch
mixers and twin-screw extruders, morphology development mechanisms are
similar and the final morphology at matched conditions is also similar
[260,322]. It is also important to note that researchers using batch mixers [293]
and those using twin screw extruders [292] achieved similar morphologies,
mechanisms and conclusions about the polymer blending process. However,
many laboratories, especially those at Universities, have used miniature
mixtures to simulate larger scale mixers. One of the most popular miniature
mixers is the Minimax mixer [340].
1.9.2.4.6 Model experiments
Because of the difficulty in following a particle in the complex flow
paths of a twin-screw extruder or twin-rotor batch mixer, several
researchers have used model flow fields to study polymer blending [251253,256,263,307-309,341,342]. Fig. 1.29 shows that polymer pellet break
up via sheeting is seen even in simple shear flows and it was confirmed that
this type of deformation occurs in the melt state [251,253,256].
Figure 1.29: Sheeting mechanism in the melt state. A sheet formed when
a polypropylene pellet in a polystyrene matrix is subjected to
a shear flow in parallel plates
Using this model experiments, researchers were able to investigate
the critical parameters responsible for break up and have developed rules to
Introduction
67
Chapter 1
68
Viscosity ratio
K d T , J , M d 0
Kc T , J , M c 0
oO
Kd r T , J , M d r
K c T , J , M c 0
..(1.28)
J dc
J dc o 1 / 6 R>V 11 V 22 d V 11 V 22 @c o
J cr
J dc or 1 / 6 R>V 11 V 22 d r V 11 V 22 c @
(1.29)
Capillary number
k
K.J .R
o kr
J
dc
K * .J .R r
J dc r
..(1.30)
Introduction
69
Dr
A(t )
A0
(1.31)
Chapter 1
70
In zone III, the cross-linked rubber particles now have a very high
viscosity, and further dispersion of these particles by the stress transferred
by the low viscous thermoplastic matrix will be impossible. After the cross-
Introduction
71
Chapter 1
72
Introduction
73
Chapter 1
74
Study of the water diffusion of the nylon/EPDM blends and the effect
of compatibilisation, crosslinking and temperature on the diffusion
behaviour.
Introduction
75
1.11 References
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
Chapter 1
76
13.
14.
15.
16.
17.
Z H.S Moon, S Hyun, W.M Choi, J Appl. Polym. Sci. 104, 95, 2007.
18.
19.
20.
21.
22.
23.
24.
25.
26.
H.Z. Liu, T.X. Xie, Y. Zhang, J. Polym. Sci. Polym. Phys. 44, 1050, 2006.
27.
28.
29.
30.
31.
Introduction
77
32.
33.
34.
35.
36.
37.
38.
G.D. Merfeld, D.R. Paul, in Polymer Blends, Vol.1, D.R. Paul, C.B.
Bucknall, Eds, Wiley Interscience, New York, 2000.
39.
40.
41.
42.
43.
44.
45.
46.
47.
Chapter 1
78
48.
49.
50.
51.
R. Ashaletha, M.G. Kumaran, S. Thomas, Eur. Polym. J., 35, 253, 1999.
52.
53.
Z. Oommen, M.R.G. Nair, S. Thomas, Polym. Eng. Sci., 36, 151, 1996.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
Introduction
79
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
Chapter 1
80
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
89.
90.
R. Fayt, R. Jerome and P.H.Teyssie, J. Polym. Sci., Polym. Lett. Ed., 24,
25, 1981.
91.
92.
93.
94.
Introduction
95.
81
96.
97.
G. Riess, Y. Jolivet, Am. Chem. Soc. Adv. Chem. Ser., 142, 243, 1975.
98.
99.
Chapter 1
82
111. D.R. Paul, G.E. Locke, J. Appl. Polym. Sci., 17, 2791, 1973.
112. D.R. Paul, C.R Lindsey, J.W.Burton, J. Appl. Polym. Sci., 26, 1,1981.
113. B.G. Soares, A.S. Sirqueria, M.G. Oliveira, M.S.M Almeida, Macromol.
Symp., 189, 45, 2002.
114. D.F. Ferrari and W.E Baker, J. Polym. Sci. Part A: Polym. Chem., 36,
1572, 1998.
115. W.B. Baker, C.E Scott, G.H.Hu eds., Reactive Polymer Blending,
Hanser, Munich, 2001.
116. C.G. Hagberg, J.L. Dickerson, J.L Plast. Eng. 53, 41,1997.
117. J. Xueliang, Z. Yong; Z. Yinxi. J. Polym. Sci., Part B: Polym. Phy. 42,
1181, 2004.
118. R.Gadekar, A.Kulkarni, J.P Jog, J. Appl. Polym. Sci. 69, 161,1998.
119. C. Pagnoulle, R.Jerome, Polyblends 97, Brookfield, 7,1997.
120. Y. Seo, J. Appl. Polym. Sci., 64, 359, 1997.
121. C.C. Chen, J.L.White, Polym. Eng. Sci., 33,923,1993.
122. S. Balakrishnan, N.R. Neelakandan, D.N. Saheb, J. Pjog, Polymer, 39,
5765, 1998.
123. J.R.J. Campbell, S.Y.Hobbs, T.J. Shea, V.H. Whatkins, Polym. Eng.
Sci., 30, 1056, 1990.
124. D. Maeder, J. Kressler, M. Weber, Macromol. Symp., 112, 123,1996.
125. S.A. Madbouly, J.U. Otaigbe, T.Ougizawa, Macromol. Chem. Phys.,
207, 1233, 2006.
126. S.L. Sun, Z.Y. Tan, M.Y. Zhang, Polym. Int., 55, 834, 2006.
127. Y. Li, T. Xie, G. Yang, J. Appl. Polym. Sci., 95, 1354, 2005.
Introduction
83
Chapter 1
84
148. R.A. Kudva, H. Keskkula, D.R. Paul, Polymer, 39, 2447, 1998.
149. A. Tedesco, R.V. Barbosa, S.M.B. Nachtigall, R.S. Mauler, Polym.
Test., 21, 11, 2002.
150. V. Chiono, S. Filippi, H. Yordanov, L. Minkova, P. Magagnini,
Polymer, 44, 2423, 2003.
151. J.K. Kim, S. Kim, C.E. Park, Polymer, 38, 1809, 1997.
152. J.K. Kim, S. Kim, C.E. Park, Polymer, 38, 2155, 1997.
153. J.K. Kim, D.K. Yee, H.K. Jeon, C.E. Park, Polymer, 40, 2739, 1999.
154. W. Hale, H. Keskkula, D.R. Paul, Polymer, 40, 365, 1999.
155. B.K Kim, S.Y Park, S.J Park, Eur. Polym. J., 27, 349, 1991.
156. M.L. Xue, Y.L. Yu, J. Sheng, H. H. Chuah, C-H. Geng, J. Macromol.
Sci. Part B: Phys., 44, 317, 2005.
157. C.Vocke, U. Antilla, J. Seppala, J. Appl. Polym. Sci., 72, 1443, 1999.
158. S.C. Jana, N. Patel, D. Dharaiya, Polymer, 42, 8681, 2001.
159. C. Koning, M. Van Duin, C. Pagnoulle, R. Jrme, Prog. Polym. Sci., 23,
707, 1998.
160. P.S. Archondouli, N.K. Kalfoglou, Polymer, 42, 3489, 2001.
161. D.A. Costa, C.M.F. Oliveira, J. Appl. Polym. Sci., 81, 2556, 2001.
162. A. Retolaza, J.I. Eguiazabal, J. Nazabal, J. Appl. Polym. Sci., 97, 564, 2005.
163. T.G. Gopakumar, S. Ponrathnam, A. Lele, C.R. Rajan, A. Fradet,
Polymer, 40, 357, 1999.
164. H.Q. Xie, Y. Chen, W. Yang, D. Xie, J. Appl. Polym. Sci., 101, 792, 2006.
165. Y. Li, B.Y. Zhang, Z. Feng, A. Zhang, J. Appl. Polym. Sci., 83, 2749, 2002.
166. B.D.Favis, J.M Willis, J. Polym. Sci. Polym. Phys., 28, 2259,1990.
Introduction
85
167. B. Majumdar, D.R. Paul, A.J. Oshinski, Polymer, 38, 1787, 1997.
168. A.J. Oshinski, J.H. Keskkula, D.R. Paul, Polymer, 33, 284, 1992.
169. B. Majumdar, H. Keskkula, D.R. Paul, N.G. Harvey, Polymer, 35,
4263, 1994.
170. A. Gonzalez-Montiel, J.H. Keskkula, D.R. Paul, Polymer, 36, 4587,
1995.
171. A.J. Oshinski, H. Keskkula, D.R. Paul, Polymer, 37, 4909, 1996.
172. B. Majumdar, H. Keskkula, D.R. Paul, Polymer, 35, 1386, 1994.
173. B. Majumdar, H. Keskkula, D.R. Paul, Polymer, 35, 1399, 1994.
174. B. Majumdar, H. Keskkula, D.R. Paul, Polymer, 35, 3164, 1994.
175. A. Gonzalez-Montiel, A.J. Oshinski, H. Keskkula, D.R. Paul, J. Polym.
Sci. B: Polym. Phys., 33, 1751, 1995.
176. W. Loyens, G. Groeninckx, Macromol. Chem. Phys., 203, 1702, 2002.
177. A. Gonzalez-Montiel, J.H. Keskkula, D.R. Paul, Polymer, 36, 4587, 1995.
178. K. Dedecker, G. Groeninckx, Polymer, 39, 5001, 1998.
179. G. Groeninckx, C. Harrats, S. Thomas, Reactive Polymer Blending,
Eds. W.E. Baker, C.E. Scott, G.H. Hu, Hanser, Munich, 2001.
180. K. Dedecker and G. Groeninckx, J. Appl. Polym. Sci., 73, 889, 1999.
181. I. Fortenly, Z. Cerna, J. Binho, J. Kovar, J. Appl. Polym. Sci., 48, 1731,
1993.
182. K.M. Hong, J. Noolandi, Macromolecules, 13, 964, 1980.
183. K.M. Hong, J. Noolandi, Macromolecules, 14, 727, 1981.
184. K.M. Hong, J. Noolandi, Macromolecules, 14, 736, 1981.
Chapter 1
86
Introduction
87
Chapter 1
88
Introduction
89
232. C. Nakason, S. Saiwari, A. Kaesaman, Polym. Eng. and Sci., 46, 594, 2006.
233. H. Huang, T. Ikehara, T. Nishi, J. Appl. Polym. Sci., 90, 1242, 2003.
234. J. Oderkerk, G. Groeninckx, Polymer, 43, 2219, 2002.
235. J. Oderkerk, G. Groeninckx, M. Soliman, Macromolecules, 35, 3946,
2002.
236. J. Oderkerk, G. De Schaetzen, B. Goderis, L. Hellemans, G.
Groeninckx, Macromolecules, 35, 6623, 2002.
237. L.A. Utracki, in Polymer Blends Handbook, L.A. Utracki, Ed., Volume
1, Kluwer, Academic Publishers, Dordrecht, The Netherlands, 2002.
238. C.W. Macoscko, Macromol. Symp., 149, 171, 2000.
239. D. R. Paul, in polymer blends, D. R. Paul and Newman, s. Eds., Academic
Press, New York, 1978.
240. H. F. Mark, M. Bikales, C. G. Over Berger, G. Menges, J.I Kroschwitz,
Eds., Encyclopaedia of Polymer Science and Engineering, 2nd Ed., John
Wiley & Sons, New York, 1987.
241. D. R. Paul and C. B. Bucknall, Eds., Polymer Blends John Wiley &
Sons, New York, 2, 2000.
242. J.J. Elmendorp, Ph.D Thesis, Technical University, Delft, The
Netherlands, 1986.
243. H.J. Van Oene, J. Colloid interface Sci., 40, 448, 1972.
244. J. Lyngaae-Jorgensen, Org. Coat. Plast. Chem., 15, 174, 1981.
245. L.A. Utraki, Z. H. Shi, Polym. Eng. Sci., 32, 1824, 1992.
246. H.P. Grace, Chem., Eng., Commun., 14, 225, 1982.
247. F.D. Rumscheid and S. G. Mason, J. Colloid Sci., 16, 238, 1961.
Chapter 1
90
Introduction
91
Chapter 1
92
Introduction
93
Chapter 1
94
Introduction
95