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POLY(TRIMETHYLENE
s
y res
TEREPHTHALATE)––THE NEW
W
ERING
GENERATION OF ENGINEERING
E TER
THERMOPLASTIC POLYESTER
op P
C ic
C. SARATHCHANDRAN, CHIN HAN N CHAN,
TH
T AS
SITI ROZANA BT. ABD. KARIM, and SABU THOMAS
or m
th de
CONTENTS
Au ca
19.1 Poly(Trimethylene
methylene Tere
T
Terephthlate)
e ate) (PTT) ......
...
................................................ 574
19.2 Crystal
al Structure
tructure and
a Stereochemistry
an reochemistry of
o PTT ...................................... 584
A
9.6 Melting
19.6 M Temperature
erature and
mperature an Equilibrium Melting Temperature of PTT.... 597
9.7 Morphological
19.7 M
Mo Structures
Stru
Struct of PTT .......................................................... 601
Ap
19
19.8 Mechanical Properties ........................................................................... 605
19.9
19 PTT-Based Blends.................................................................................. 606
19.10 PTT Composites and Nanocomposites ................................................ 609
19.11 Conclusion ........................................................................................... 614
Keywords .......................................................................................................... 614
Acknowledgment .............................................................................................. 615
References ......................................................................................................... 615
574 Physical Chemistry of Macromolecules: Macro to Nanoscales
s
(PBT). Polyesters can be classified as thermoplastic or thermosettingng depending
pending on
y res
the chemical structures. Table 1 shows the industrial productionn of polyesters,
olyesters, and
a it
is estimated that the production will exceed 50 million tonnes
nes by the year of
o 2015.
Polyesters are made from chemical substances found mainly in petroleum
petrole
petro and are
op P
mainly manufactured into fibers, films, and plastics.. These
T se polyesters
polyeste are abbrevi-
po
ated as mGT, where m denotes the number of methylene lene groups;
ethylene ps for example, PET,
g ps;
PTT, and PBT are abbreviated as 2GT, 3GT, and nd 4GT, respectively.
resp
respe y.
C ic
or m
TABLE 1 The world production of polyester
yester
er (Adapted from
f Sirichayaporn
richayaporn
ayaporn (201
(2012))
Textile-PET 220 39
A-PET
-PET (solution casted
Resin, bottle/A-PET cca ET)
PET) 9 16
A
cial polyester
Special polyes
polyest 1 2.5
e
tal
Total 31.2 59
pl
-
Ap
s
1. Condensation Polymerization: When acid and alcohol are reacted ted in vac-
vac-
y res
uum, at high temperatures condensation polymerizationn takes After
kes place. Af
A
the polymerization, the material is extruded onto a casting troug in the
sting trough
form of ribbon. Upon cooling, the ribbon hardens into chips.
ns and is cut int
2. Melt-spun Fiber: The chips are dried completely. ely. Hopper reservoirs
r are
op P
then used to melt the chips. Afterwards, the m molten polymer is extruded
en po
poly
through spinnerets and cooled downn by air blow blowing. It is then loosely
C ic
wound around cylinders.
3. Drawing: The fibers consequently ntlyy formed are hot stretched
ched to about
tretched abou
ab five
or m
times of their original length th (to reduce the
th fiberr width).
th). This is then
th con-
verted into products.
th de
$
$$
%J
$$
$
is carried out in the presence of o hot catalyst
lyst like titanium
tita
tit butoxide (Ti(OBu)4) and
o
xidee (DBTO) at a temperature
dibutyl tin oxide emperature of 260 2 C. The important by-products
A
LQVV'X#
-
tionn of propane diol
d and TPA A is considered
consid
conside as the least economic and industrial
e
method.
thod. The reacti
reaction
re n is carried out
ou in the presence of a “heel” under a pressure
pl
of TPA (Chuah, 2001). Recent R studies by different groups show that the selec-
tion of the catalyst plays a major role on the reaction rate and PTT properties.
Commonly used catalysts like titanium (Doerr et al., 1994), tin (Kurian and Li-
C
ang, 2001; Fritz et al., 1969) and antimony (Karayannidis et al., 2003; Fitz et
al., 2000) compounds have their own limitations. Titanium-based catalysts are
active but the PTT is discolored, antimony-based catalysts are toxic and only
active in polycondensation while tin-based compounds have lower catalytic ac-
tivity. Karayannidis and co-workers (2003) reported the use of stannous octoate
([CH3(CH2)3CH(C2H5)COO]2Sn) as the catalyst for PTT synthesis but its catalytic
?
$
%
576 Physical Chemistry of Macromolecules: Macro to Nanoscales
s
g mL–1 PTT solution of 1,1,2,2-tetrachloroethane/phenol (50/50, w/w)) mixture.
y res
The CTCG was determined by titrating 25 mL of chloroform and a few drops of
phenolphthalein indicator to a solution of 1.000 g of PTT and d 25 mL of bbenzyl
alcohol against a titer of 0.561 g of KOH in 1 L of benzyl yl alcohol.
Works by different groups show that stannous oxalate ate (SnC
(Sn 2O4) is one of the
op P
best for PET (Fitz et al., 2000) and PBT (Paul, 1989) 989) ssyntheses
heses aand also a poten-
hese
tial additive for improving the properties of the polymers (Corbiere
he polymer ere and Mosse,
C ic
1953). Studies by Yong et al. (2008) who used SnC2O4 as the catalyst
PTT, the results show that SnC2O4 displayslayss higher polymerization
poly
atalystt to synthesis
zation
on activity tha
than the
or m
other catalysts which is clear by thehe factt that SnC
Sn 2O4 shows
hows the highest int intrinsic
i
viscosity ([K]) and lowest CTCGs CGs (ref. Table 2). Decrease
ecrease
ase in reaction
react time and
th de
enhancement of [K] of PTT are observed aas shown wn in Table 2 and Figure
F 1 when
SnC2O4 is used as catalyst.
yst. Higher catalytic
catal
cata activity
tivity
vity of SnC
Sn 2O4 is attributed to its
chelate molecular structure suggests SnC
ucturee and sug
sugg nC2O4 ass a more
mor promising
pr catalyst for
Au ca
PTT
Catalyst
C
Catal viscosity ([]) (content of ter- esterification
(dL g–1) minal carboxyl (DE) after 1.8
groups) hr
s
C
a
–4
used was 5·10 mol/mol of TPATPA. Parameter
meter DE denotes
denote degree of esterification (Adapted
from Yong andd co-workers
o-workers (2008)).
(20
(2
th
e
pl
Ap
In the industrial synthesis, the process of melt polycondensation has the dis-
?
?
?
\$
which often limits the desirable molecular weight of the polymer. Specially y de-
ally de
signed reactor (e.g. disk-ring reactor) is required for the melt polycondensation ondensation
sation
s
process in most cases, by providing large liquid surface area with the application
y res
of high vacuum for rapid removal of by-products. Young et al. l. (2012)
2012) propos
proposed
propo
the use of solid-state polymerization as a potential technique iquee to overcom
overco
overcome the
limitations of the melt polycondensation process. For the he synthesis of PTT, low
$L$$X
<
<
<
op P
$
$$
$
pelletized and is crystallized to prevent particle cle agglomeration during
le agglomera
agglome rin solid state
C ic
polymerization, with subsequent heating to a temperature above
tion temperature (Tg) and below the melting elting
ng temperatu
temperat
glass transi-
ve the gla
gl
temperature (Tm) of the pre po polymer
or m
(Lee et al., 2010). This is explained d on the
he basis ofo negligible resistance
giblee diffusion resis
re
<$
?
<
<$
th de
when the pre polymer is used, ed, which has zero ze carboxylic
boxylic acid content.
rboxylic conten
Although PTT is reported ed in the early
orted earl 1950s,
ear s, interest in commercialization
comm of
PTT began with the introduction
duction oof relatively
velyy new methods for the synthesis of
w metho
Au ca
yingg PT
of studying PTT for
or en ring
engineeringng applicatio
application
applications (DuPont, 2011; Haas et al., 2005).
The PTT is rapidly
ra crystallizing
allizing linear
line
lin aromatic polyester. Differential scan-
e
calorimete ((DSC)
ningg calorimeter SC) studies by Hong et al. (2002) using completely amor-
pl
phous PTT ( M n = 43,000 g mol–1) prepared by heating the sample to 280oC and
quenching (at a cooling
then que
quench coo rate of 200oC min–1) to room temperature, shows
Ap
o
that the Tg lies between 45–65
4
45 C, followed by melt crystallization exotherm and
o
then Tm at 230 C. The completely amorphous nature of the PTT prepared by rapid
quenching
q from 280o
$
_\
where the sample exhibits only amorphous scattering without any crystalline scat-
tering. It is common that the Tg
%
PTT with linear heating rate after rapid quenching from the molten state of PTT.
The injection molded PTT (Mw = 22,500 g mol–1 and polydipersity (PI) = 2.5)
after rapid quenching from the molten state was subjected to an underlying heat-
`q> = 2oC min–1, a period of 60 s, and an amplitude of ± 1.272oC in the
temperature range from –50 to 150oC. The Tg observed in the reheating cycle is
Poly(Trimethylene Terephthalate)––The New Generation of Engineering 579
50.6o
$
L|Cp) at 0.20 J g–1 oC–1. The thermogram
for the reheating cycle for this injection molded PTT is shown in Figure 3.
s
es
Au c
o
A
temperature
perature range from –50 to 10000oC.
e
rimetry, standard
stan DSC
SC and temperature-modulated
tem differential scanning calorim-
Ap
3RAo Cp 2 (exp)
Cp (exp) − Cv (exp) = (1)
T
Cv (exp) o
T m
580 Physical Chemistry of Macromolecules: Macro to Nanoscales
s
ity linked to the group and skeletal vibration, which is then fitted to the he general
y res
Tarasov function (Pyda et al., 1998; Tarasov and Khimi, 1950).
In order to obtain the 3 characteristic parameters Θ1, Θ2 and nd Θ3 wher
where Θ =
wh
hQ/kB (h is the Planck’s constant, Q is the frequency, and kB is the B Boltzmann
constant). The functions D1, D2, and D3 are the one-,, two-, and three- t dimen-
op P
sional Debye functions (Wunderlich, 1990; Wunderlich, derlich 1995).
995). T
995) The characteristic
temperature Θ3 describes the skeletal contributions butions with a quadratic at frequency
C ic
distribution and for linear macromolecules,
K. Pyda et al. (1998) also suggested that
he value of Θ3 is between
s, the
at knowing Θ1, Θ2 and
etweenen 0 and 150
d Θ3?
?
?
or m
skeletal heat capacities and with a list off group vi vvibrations,
ons, one can easily
easil calcu-
late the heat capacity at constant nt volume for th the solidid state polymer, which
tate of a polym
po
th de
⎛Θ Θ Θ ⎞ ⎛ Θ ⎞ ⎛ Θ ⎞⎡ ⎛ Θ ⎞ ⎛ Θ ⎞⎤ ⎛ Θ ⎞ ⎡ ⎛ Θ ⎞ ⎛ Θ ⎞⎤
2
Cv ( sk )
pl
= T ⎜ 1 , 2 , 3 ⎟ = D1 ⎜ 1 ⎟ − ⎜ 2 ⎟ ⎢ D1 ⎜ 2 ⎟ − D2 ⎜ 2 ⎟ ⎥ − ⎜ 3 ⎟ ⎢ D2 ⎜ 3 ⎟ − D3 ⎜ 3 ⎟ ⎥ (2)
NR ⎝ T T T ⎠ T Θ
⎝ ⎠ ⎝ 1 ⎠⎣ ⎝ T ⎠ ⎝ T Θ Θ
⎠⎦ ⎝ 1 2 ⎠ ⎣ ⎝ T ⎠ ⎝ T ⎠⎦
Ap
The mechanical and electrical properties of PTT are close to PET, and even
Th
when
whh these polyesters show lower mechanical properties as compared to Nylons,
they show better elelctrical properties. The thermal stability of PTT by referring
to the onset of decomposition temperature using thermal gravimetry analyzer
(TGA), is comparable to polycarbonates (PC) (compare to Tables 3, 4 and Figure
4). Thermogram in Figure 4 shows that PTT is thermally stable up to 373oC with
1.5 wt% of mass loss when it was heated up at 30oC min–1 in nitrogen atmosphere.
PTT thermally degrades further at around 494oC with 92 wt% of mass loss and the
remaining 4 wt% of mass fully decomposes at 600oC.
Poly(Trimethylene Terephthalate)––The New Generation of Engineering 581
TABLE 3 Some physical properties of PTT with other polyesters and nylon (Adapted
from Hwo (1998))
s
Specific Gravity (mea-
sured as per ASTM 1.40 1.35 1.34 1.14 1.200 1.14
y res
D792 specifications)
Tm (oC)
(Using DSC for injec-
tion molded samples at 265 227 228 265 -- 230
op P
a heating rate of 10oC
min-1*)
C ic
Tg* (oC) 80 45–60 25
5 50–90 150
50 50
Onset of decomposi-
or m
tion temperature by 350 373 378 375
3 -- 398
39
using TGA (oC)
th de
TABLE 4 The other physical properties of PTT (Adapted from Brown and co-workers
(1997))
Properties Values
s
Equilibrium melting point (oC) 248 (Lin, 2007; Dangseeyun
eeyun
un et
y res
al., 2004), 252 (Srimoaon
moaon n et al.,
2004), 237 (Pydaa et al., 1998
1998)
L|Hf) (kJ mol–1) 30 ± 2
op P
Fully amorphous heat capacity (J K–1 94
mol–1)
r C ic
Crystallization half time at 180oC (min)
65
6
4
Crystallization of PTT takes place below the Tm and above the Tg of PTT. At
temperature below Tm, crystallization of PTT is driven by thermodynamics and
at temperature below Tg crystallization ceases due to lack of segmental mobility
of PTT chains. The Tm of PTT can be determined by examining the variation ion in
s
%
: LQVVX LQVVX
VX studied
y res
this relation (variation of density of PTT upon heating or/and cooling)oling) by us using
usi
atomistic simulations, where the molecular dynamic simulation tion was used tto deter-
mine the properties of PTT down to the molecular level.. The variation oof density
with respect to temperature as observed by Lin (2007) is shown in Figure F 5. The
op P
reported Tm of PTT (with an entanglement Mw betwe between 4900–5000
4900
4900– g mol–1) is
around 227–277oC and Tg is around 102oC. Experimentally
perimentally observed d vvalues for Tm
C ic
o o
is in the range of 226–230 C, and Tg is between
ween 45–65 C C. The marked ed difference
d
in estimated Tm and Tg by using atomistic
stic simulations and DSC,, respectively
respecti
respectively, can
m
12o
1 –1
be attributed to the extremely fast cooling
ng rate (1
(10 C s ) forr the former an analysis
and much slower rate for the later.
er
er.
de
pl
Ap
FIGURE 5 The variation of density of PTT fiber with respect to temperature on heating
() and cooling (), as per the molecular dynamics simulation studies done by Lin (2007)
(Modified from Lin (2007)).
584 Physical Chemistry of Macromolecules: Macro to Nanoscales
s
3GT where the crystalline PTT has gauche and trans conformations. ions. The chain
ch
y res
conformation of the PTT fiber changes reversibly between two orms when the
wo forms
fiber is strained. This can be followed by using the techniques ues of X-ray diffraction
dif
(XRD). In the unstrained form, the methylene section of the PTT chain cch has the
op P
conformation of gauche-trans-gauche; upon straining in thisis conformation
conform
co changes
to trans-trans-trans (Hall and Pass, 1976) .
The crystal structure and unit cell dimensions sions using the
ensions th techniques
qu of XRD
hniqu
C ic
were reported by Desborough et al. (1979), 9), PTT
TT was me melt spun
mel
%
+'
'
+'
+'
n at 270oCC, fo
'
followed
'oC for 2
or m
_=#$
$
α
α radiation
radiati with
camera of the type as described edd by Elliot (1965).
(19
( A highly monochromatic
monochrom
monochr beam
th de
of X-ray of 40 μm with short hort exposure ti time was ass applied. The XRXRD photograph
$
$
$
Au ca
Each
ach of them
th iss slightlyly displaced to either side of the meridian and the ab-
e
sence
ence
ce of layer line
l leads
ds too the suggestion
sugges that the unit cell is triclinic. Later on,
this
is suggest
suggestion w was further support
supported by Ho et al. (2000) and Yang et al. (2001).
pl
Study by DesDesboroughugh et al. (19(1979) shows that a comparison between the density
alculate from the unit
calculated nit ccell dimensions with the theoretical values from litera-
it cel
Ap
tures; points
ture p to the existence of two monomers per unit cell and there is one mo-
lecular chain with two monomers per crystallographic repeat as suggested in Fig-
lec
ure 7. Based on these assumptions and using studies by Perez and Brisse (1975,
1976, and 1977) as a guide they calculated the bond lengths and bond angles as
shown in Table 5.
Poly(Trimethylene Terephthalate)––The New Generation of Engineering 585
TABLE 5 The values of bond length and bond angle of PTT fiber as calculated by
Desborough et al. (1979) (Adapted from Desborough and co-workers (1979))
o
Bond Length ( A ) egree)
Angle (degree)
s
y res
Co-C1 1.39 α1 120
op P
H1-C1 1.07 α4 120
C ic
C4-C3 1.48 α6 113
or m
O1-C4 1.21 α7 12
122
O2-C4 1.34
.34
34 α8 1
116
th de
C5-O2 1.44
44 α9 106
C6-C5 11.54
A
e
pl
Ap
FIGURE 6 Diffraction patterns of PTT fibre drawn so as to reduce the tilt (tilted crystal
orientation refers to the position in which the unit cell is tilted away from its usual
orientation as compared to the situation where chain and fiber axes coincident).
s
y res
op P
FIGURE 7 Crystallographic repeat of PTT fiber based
sed on tthe X-ray
X-ra studies carried out
by Desborough et al. (1979).
C ic
Source: Reproduced from Desborough andd co-workers,
sion of Elsevier Ltd.
o-workers, copyright
co ht (1979),
9), by
b permis-
or m
The length ratio between c-axiss off the unit cell and the he extended chain length
le
l of
PTT is found to be about 75% indicating
dicating a big alo the c-axis,
bi zigzagg conformation along
th de
defor
which has been suggested as the high deformability ityy in crystals when
wh drawn, and this
explains why slight deviation on in unit cell
viation ce dimensions
e ons ns are usually
usu observed by differ-
Au ca
$
%
%
compared to other her polyesters, which
w iss evidenced
videnced by the exceptional use of PTT as
$$
$
J
$
$$
$$
$
J
J
A
TABLE
ABLE 6 The preparativeive
ve co
conditions of PTT and the corresponding lattice constants of
triclinic unit cell
the tricl
A
Melt spun at
270oC, fol-
lowed by cold (Elliot,
drawn at a draw Electron dif- 1965)
4.5 6.2 18 98 90 111
ratio of 4:1 and fraction
then annealed
at 185oC for
2 hr.
Poly(Trimethylene Terephthalate)––The New Generation of Engineering 587
TABLE 6 (Continued)
all,
(Hall,
Melt polymer- Electron dif- 4)
1984)
4.6 6.2 18 98 90 111
ization fraction
s
Confined
y res
thin film melt ectron
Electronn
polymeriza- raction
diffraction
(
(Y
(Yang et
tion (CTFMP) 4.5 6.2 19 97 92 111 CERIU
CERIUS
al., 2001)
at tempera- simulatio
simulation
tures between pr
program
program.
op P
150–220oC
Bulk polymer-
C ic
ization (Yang et
4.6 6.4 19 99 92 11
112 AXD
WAXD
o
(180 C and a 2001)
al.,
72 hr)
or m
Polycondensa-
tion reaction (Wang et
e
0.46 0.61 1.9 98 92 110 WAXD
between TPA al., 2001)
and 1,3-PDO
ad
Ac
e
pl
Ap
FIGURE 8 Atomic positions of melt-spun PTT chains with triclinic crystal unit cell
determined by wide-angle X-ray diffraction (WAXD) by Wang et al. (2001).
s
–1
bands of IR between 1750–800 cm are helpful to estimate thee fraction tion of the
y res
crystalline phase of PTT samples. The assignment of the absorption
on bands in this
orption
region for PTT was proposed by Yamen et al. (2008) (Tablele 7).
op P
TABLE 7 Wavenumbers and assignments of IR band d ex
exhibit
it by PTT as proposed by
Yamen et al. (2008) (Adapted from Yamen and co-workers
orkers (2008)))
rs (2
(20
C ic Wavenumber (cm–1)
Assignment
Ass
Assi nt
or m
Amorphous phase Crystalline phasee
1577 (weak) - -
Au ca
1504 (medium) (m
1504 (medium) matic
aromatic
um))
1467 (medium) 146 (medium)
1465 dium) Gauche CH2
A
1456 (medi
(medium)) - Trans CH2
1400
400 (medium
(medium) - aromatic
e
1385 (mediu
(medium) - Trans CH2 wagging
pl
1173
117 (weak) -
TABLE 7 (Continued)
937 (weak) 937 (weak)
s
y res
The FTIR spectroscopy studies on PTT (refer Figure 9) subjected cted to isot
isother-
o
mal crystallization for 40 min at 200 C, shows the following
wing result. The area ra-
gned to the % of gauche
tio of the absorption band (A1358/A1504), which is assigned
op P
conformation, is calculated to be 1.39 while the ratio
tio (A9766/A1504), which denotes
the trans conformation of the methylene groups found to
ps iss foun
fou o bbe 0.28, indicating
reasonable amount of crystallinity in the sample
mple Table 8). The ccrystallinity
ple (refer Ta
Tab
C ic
estimated by DSC analysis after isothermal
shows a value of 40.8%.
rmal crystallization
crystalliza 00oC fo
at 200 for 40 min
or m
TABLE 8 T crystallized at 200oC for 40
Peak assignment of PTT
TT 0 min
th de
Amorphous Crystalline
ystalline
line Assignment
ment
nt
1578 (weak) - -
1505 (medium)
m) 1504 (medium)
m) aromatic
aromati
A
1464 (medium
(medium) medium)
dium)
1465 (medium) Gauche CH2
Gau
Ga
1408
08 (medium) - aromatic
e
1389 (medi
(medium) - Trans CH2 wagging
pl
1358
358 Gauche CH2 wagging ( both crystalline and
amorphous)
Ap
10 (shoulder)
104
1040 1043 (shoulder) C-O stretching
933 (shoulder) 933 (shoulder) CH2 rocking (both crystalline and amor-
phous)
s
e
t
Au
FIGURE
IGURE 9 The FTIR
IR PT crystallized at 200oC for 40 min.
R analysis of PTT
pl
19.4
9.4 KINETICS
K
KIN OF
F ISOT
ISOTHERMAL
SO CRYSTALLIZATION OF PTT
Ap
The overall
o rate of isothermal crystallization of PTT (semicrystalline polymer)
can be monitored by thermal analysis through the evolution of heat of crystalliza-
ca
tion by DSC as depicted in Figure 10. The sample is isothermally crystallized at
preselected crystallization temperature (Tc) until complete crystallization. Half
time of crystallization (t0.5) for the polymer is estimated from the area of the exo-
therm at Tc = const, where it is the time taken for 50% of the crystallinity of the
crystallizable component to develop. The rate of crystallization of PTT can be
easily characterized by the experimentally determined reciprocal half time, (t0.5)–1.
Poly(Trimethylene Terephthalate)––The New Generation of Engineering 591
s
y es
op
th de
The crystallization
allization
ization kinetic
kinetics in polymers
olymers
ers under isothermal
i conditions can be best
A
X (t ) = 1 − exp ⎡⎣ − K A1/n ( t − to ) ⎤⎦
n
pl
(3)
Ap
11 with KA1/n = 0.07 min–1 and n = 3.9. A comparison of our results with that of
Hong et al. (2002) (Table 9) shows a clear difference in the Avrami exponent and
olecula
rate constant which can be explained on the basis of the differences in molecular
weights of the two samples and also on the basis of the rate of coolingg applied.
ied.
s
y res
TABLE 9 The values of Avrami parameters, KA1/n and n, for crystallized
zed PTT as presen
presented
by Hong et al. (2002) (Adapted from Hong and co-workers (2002)))
op P
Tc (oC) KA1/n (min–1) n Tc (oC) KA1/n
1
(min––11) n
190 43
0.43 3.0
3 0 - - -
Au ca
195 24
0.24 3.0 - - -
200 0
0.0
0.010 2.9 - - -
A
2205 1
0.0011 2.9 - - -
e
210 10–6
5.8.10 32
3.2 - - -
pl
–1
kcal m
kca mol . Hong et al. (2002) studied the isothermal crystallization kinetics of
TT The DSC analyses were done by melting the samples at 280oC for 5 min
PTT
PTT.
and then rapidly cooling with a rate at 200oC min–1 to an ambient Tc. For the
isothermal cold crystallization, the samples were melted at 280oC and then rap-
idly cooled to low temperatures using liquid nitrogen so as to get a completely
amorphous sample. Avrami model can be adopted to describe primary stage of
isothermal crystallization from the melt and glass states adequately. Impingement
of the PTT spherulites during the secondary state of the crystallization leads to the
deviation from the Avrami model. The values for Avrami parameters as observed
by Hong et al. (2002) are given in Table 9.
Poly(Trimethylene Terephthalate)––The New Generation of Engineering 593
s
Au ca
or
2
ts the
curve represents he regressi ve after Eq. (3) ((r = 0.9967).
regression curve
th
The Avrami exp exponentnt values vary bbetween 2 and 3 corresponding to different
e
values of 5 corresponds
nent valu sponds to a solid sheaf like growth and athermal nucleation
orresponds
for cold crystallization.
cr n. They
Th reported that the regime I-II and regime II-III transi-
Ap
tions occur
tion o at temperatures of 215 and 195oC, respectively. The crystallite mor-
phologies
pho
ho of PTT from the melt and cold crystallizations exhibit typical negative
spherulite and sheaf-like crystallite, respectively. The regime I-II-III transition
is accompanied by morphological change from axialite-like or elliptical-shaped
crystallite to banded spherulite and then non-banded spherulite. This is interest-
ing to compare the Avrami exponents and the rate constants after Avrami model
for isothermal crystallization kinetics of PET, PBT, and PTT (Dangseeyun et al.,
2004) (refer Table 10). At Tc = const, the rate constant (KA1/n) of PBT > PTT >
PET.
TABLE 10 The Avrami exponents
onents
nts and the rate
ra constants
co after Avrami model for isothermal crystallization kinetics of PET, PBT, and PTT
594
Ap
(Adapted from Dangseeyun and coo workers
pl kers (2004)
(200
s
TABLE 10 (Continued)
Ap
194 1.6 1.7 0.52 0.9994 1.4 2.0 0.63 0.9998 0.78 2.0 1.1 0.9995
pl
e
196 1.7 1.9 0.49 0.9990
0.99 1.6 2.3 0.55 0.9998 0.88 1.7 0.92 0.9993
A
198 2.0 1.7 0.41 0.9988
0.99 2.22 2.0 0.39 0.9999 1.3 1.6 0.64 0.9993
s
TABLE 10 (Continued)
pp 596
th de
or m
C ic
op P
y res
Physical Chemistry of Macromolecules: Macro to Nanoscales
s
Poly(Trimethylene Terephthalate)––The New Generation of Engineering 597
s
time for all cases. The radial growth rate of the PTT spherulite is shownn in Figure
Fig
es
12 (Hong et al., 2002). The radial growth rate of the PTT spherulite ulite decreases
decre
o
exponentially with increasing isothermal Tc from 163 to 22121 C.
Pr
pl
Ap
s
after Hoffman–Weeks (Hoffman and Weeks, 1962). Under this procedure,cedure, crystal--
re, crystal
y res
lization and melting of polymers proceed under non-equilibrium um conditions bbut
near to equilibrium. The sample is isothermally crystallized ed in a range oof (Tc).
Half time of crystallization (t0.5) for the polymer is determined
termined as described
des
de in
previous section. Subsequently, the sample is allowed to crystallize again at the
op P
same range of Tc’s for equivalent period of time until
ntil complete
co lete cr
crystallization and
the corresponding Tms are obtained from thee peak of th the endotherms
er from the
C ic
DSC traces. The Hoffman–Weeks theory (Hoffman
calculating the equilibrium melting temperature
offman and Weeks,
erature values
mperature
W s, 1962)
value for polymers
2) facilitates
ymers from
f
fro the t Tc.
or m
The equation is written as:
th de
1 ⎛ 1⎞ o
Tm = Tc + ⎜⎜1 + ⎟⎟⎟T
T m (4)
γ ⎝ γ ⎠
Au ca
angseeyun et al.,
Dangseeyun al 2004;
004; Lustinger et al., 1989), except Chung et al. (2000) sug-
pl
o
TT is 252oC.
gests the T m ffor PTT C
Srim
Srimoa 004)
Srimoaon et al. (2004)04) eevaluated the melting behavior of PTT (Figures13 (c)
Ap
and 14 (a) (b)) at different heating rates using DSC and crystallite structures using
WAXD, meanwhile Hong et al. (2002) studied the crystallinity and morphology
WA
of PTT. Generally, multiple melting peaks are related to various reasons for ex-
ample:
1. Formation of various crystal structures or dual lamellar stacking during
the primary crystallization.
2. Secondary crystallization and recrystallization or reorganization during
the heating.
3. Reorganization of the metastable crystals formed during heating resulting
in crystal perfection and/or crystal thickening.
Poly(Trimethylene Terephthalate)––The New Generation of Engineering 599
4. Multiple melting peaks are observed when the polymer exhibits polymor-
phism like nylon 6, 6 and isotactic poly(propylene) (i-PP).
ss
pyre
Ac
o
th
e
pl
Ap
FIGURE 13 (a) The XRD pattern of PTT (b) DSC trace for completely amorphous PTT
(Hong et al., 2002) (c) Evaluation of WAXD pattern as a function of Tc (Srimoaon et al.,
2004) (adapted from Hong and co-workers (2002) and Srimoaon and co-workers (2004)).
600 Physical Chemistry of Macromolecules: Macro to Nanoscales
ss
re y
op
ad
rC
Ac
e
pl
Ap
FIGURE 14 (a) The DSC traces of PTT at various Tcs (heating rate 10 oC min–1) (b)
DSC heating traces of PTT crystallized at 208 oC at various heating rates (adapted from
Srimoaon and co-workers (2004)).
Poly(Trimethylene Terephthalate)––The New Generation of Engineering 601
<
?
J?
plot at the non-linear stage where the spherulites impinge with each other. The
WAXD results by Srimoaon et al. (2004) show that there is no shift in thee 2 theta
(2T) values indicating that the unit cell of PTT does not change, ruling ing out
ut the
s
possibility of polymorphism at elevated Tcs and the formation of multiple iple peaks
y res
is explained by the presence of two populations of lamellar stacks, cks, which area
ciated
formed during the primary crystallization. This can be associated ed with the lamel-
lar branching effect for the growth of spherulites. This explanation further sup-
xplanation is fu
ported by Hong et al. (2002) optical microscopy studies. s
op P
19.7 MORPHOLOGICAL STRUCTURES OF PTT
The PTT has the unique property of forming
ly considered as arising due to chain tilting ic spherulitess and are ccommon-
ng banded sphe
ng in the lamellar
lam
la r crystals.
ystals. The banded
ba
em
structure formation in PTT has beeneen discussed in detail ail by groups. A
y different gro
gr
close analysis of the optical images
ages shows that
mages tha the formation
ation of banded
ban structure
indication with arrow as shown
ownn in Figure 15 1 (a) (Hong et al., 2002),
2002) which is de-
ad
( )
(a)
e
pl
Ap
FIGURE 15 (Continued)
602 Physical Chemistry of Macromolecules: Macro to Nanoscales
(b)
s
y res
op P
ad
C
(c)
Ac
e
pl
Ap
FIGURE 15 Optical images of PTT at (a) 210oC, (b) 215oC and (c) 217oC as observed by
Hong et al. (2002) (modified from Hong and co-workers (2002)).
Studies by Ho et al. (2000) point towards lamellar twisting as the reason for
the formation of banded spherulites in PTT. The atomic force microscopy (AFM)
Poly(Trimethylene Terephthalate)––The New Generation of Engineering 603
images for banded spherulite structure of PTT are shown in Figure 16 [as ob-
served by Wang et al. (2001)] for PTT with Mn of 28,000 g mol–1 and polydis-
$
Q
<$
%J'\$$
VQ"' LX $''QQ\
s
VoC above the melting point and then were rapidly dly cooled
y res
to the required Tc and then quenched in liquid nitrogen followed ed by observation
observat
observati
$ <
$
lamellae develop a wave-like morphology. The twisting mechanism is eevidenced
by the observation of wave-like morphology from polarized arized optical
optica microscope
op P
$
C ic
proposed by Ho et al. (2000) is shown in Figure
the direction of rotation axis is parallel to the
ure 17. Extinction
Extin n takess place
Exti
he transmitted
transmitt light
pla
p
ht off polarized
when
polarize optical
o
m
microscope.
de
e
pl
Ap
FIGURE 16 (Continued)
604 Physical Chemistry of Macromolecules: Macro to Nanoscales
ss
re y
op
ad
C
e
pl
Ap
FIGURE 16 The AFM images of the banded spherulites in PTT (a) a regular spherulite
(b) a spherulite with a band started at the primary nucleation site and (c) spherulite with
band defects along the radial direction (Wang et al., 2001). Reproduced from Wang and
co-workers, copyright (2001), by permission of Elsevier Science Ltd.
Poly(Trimethylene Terephthalate)––The New Generation of Engineering 605
s
y res
op P
or m
FIGURE 17 Schematic representation
ation of (a) the llam
lamellar geometry
metry of PTT single
sin crystal
th de
and (b) the twisting mechanism of the intralamellar
intralamel model
intralam proposed by Ho et
odel in PTT, as prop
propo
al. (2000).
C
Source: Reproduced from co-workers, copyright
m Ho and cco (2000), by permission of
opyright ((2000
Au ca
The shallowow
w C-shaped and a S-shaped
shaped
ed textures
texture observed in the crest regions
A
?
$L&X
works of Lustiger
Lusti r et al.
Lust a (1989)
89)) and Ho et al.
a (2000) speculates that C-shapes and
\$
-
$
$
e
plete rotations.
ete helical ro
rotati s. This helical cconformation accounts for the lower modulus
pl
compared
of PTT as ccom ed to PET.
Ap
Notched
Flexural Tensile Elongation
impact
Polymer modulus strength at break Ref.
s
strength
(GPa) (MPa) (%)
(J m–1)
y res
Melt-spun
- 7 (Xue et al.
al., 2007)
PTT
Hot-press (Brow
ro et al.,
(Brown
op P
2.76 59.3 - 48
PTT 19
1997)
(Brown et al.,
PET 3.11 61.7 - 37
3
1997))
PBT 2.34
C ic
56.5 - 553
(Brown
Brown eet al
al.,
m
1997
1997)
de
e
pl
Ap
(Huang and Chang, 2000), poor optical properties, and pronounced britilleness at
low temperatures. Enhancement of properties for PTT can be achieved by chang-
ing the maromolecular architecture and/or be extended by blending with existing
polymers. Polymer blends allow combining the useful properties of different
fferent nt par-
par-
s
ent polymers to be done through physical rather than chemical means.ns. Itt is a quick
y res
and economical alternative as well as a popular industrial practice
ice as compared to
direct synthesis in producing specialized polymer systems.
Table 12 summarizes selected PTT/elastomer and PTT/thermoplastic
PTT/thermoplas blends
followed by the reason(s) for the blending. The purposes
es for the blending
blen in these
op P
cases point toward two directions: i) toughening the ma
matrix second component
x of se
with dispersed phase of PTT and ii) increase the
he strength of
o PTT matrix
mat with dis-
TABLE 12 C ic
persed phase of the second component.
The PTT-based blends.
or m
Blends Reason(s) for blending Ref.
f.
th de
PTT/elastome ds
PTT/elastomer blends
PTT/ABS Acrylonitrile-bu
rylonitrile-bu yrene
Acrylonitrile-butadiene-styrenerene (Xu et al.,
(Xue a 2007)
ABS) is as
(ABS) ass
associated d with
ith good
od
Au ca
processabil
processability, mensional
iona ssta-
dimensional
an high impact
bility, and pact strength
strengt at
ratures..
lower temperatures.
A
PDM
PTT/EPDM ve the toughness of the ther-
Improve (Ravikumar et al., 2005)
plasticc
moplastic
e
PTT/therm
PTT/thermoplastic blends
pl
P
PT
PTT/PEI Improve the optical properties and (Ramiro et al., 2003)
mechanical properties
Xue et al. (2007) studied the PTT/ABS blend system in detail. Blends were
prepared in a 35 mm twin screw extruder at the barrel temperature between 245–
255oC at a screw speed of 144 rpm. Two separate Tgs in the DSC thermogram
608 Physical Chemistry of Macromolecules: Macro to Nanoscales
indicate that the blends are phase separated in the molten state. First glass transi-
tions is observed at lower temperatures between 40–46oC, which is attributed to
the Tg of the PTT amorphous phase, while the second glass transitions att higher g
o
temperatures between 100–103 C is attributed to the SAN phase. Increasing reasing
ng the
s
ABS content causes an increase in Tg of the PTT phase, whereas the Tg of the ABS
y res
phase decreases with the addition of PTT indicating that PTT is partially miscible
rtially miscib
misci
with ABS and miscibility can be improved with the addition n of ABS cont
conten De-
content.
o
crease in Tm of the PTT phase (226 to 224 C) indicates that the solubili solubilit
solubility of ABS
in PTT phase slightly increases with ascending ABS content. Epo Epoxy resin and
op P
styrene-butadiene-maleic (SBM) anhydride copolymer olymer were used as compatibil-
ere u
use
izer. As the epoxy content is increased from 1 to 3 wt% the t cold crystallization
cr
C ic
temperature (Tcc) of PTT shifts to higher temperatures
content, a decrease in Tcc of the PTT is observed.
peratures wh
erved. PTT/
while for
PTT/ABS
PTT
or 5 wt% of epoxy
blends
ds with 3 wt%
w of
or m
SBM shows a similar effect to thatt of 1 wt% epoxy epox system,
ep stem, indicating the
th com-
patibilization of SBM to PTT/ABS ABS blends.
th de
Studies by Ravikumar ett al.. (2005) show sho that att PTT/ethylene propylene
pro diene
monomer (EPDM) blends ds are immiscible,
immiscib
immisci which
chh is supported
suppo by
b an increase in
the free volume and stancy in ccrystallinity
d constancy y off PTT with increasing EPDM
llinity
Au ca
ccauses the decrease in the Tg of the PTT rich phase. The DMA shows that the ad-
$
Tg of the PTT rich
phase from around 70 to 90oC while the Tg of the PC rich phase decreases from
around 130 to around 110oC. Morphological studies using SEM and TEM show
$
Huang et al. (2002) studied the miscibility and melting characteristics of
PTT/PEI blend systems. The DSC studies show that the miscible blends show
single and compositional-dependent Tg over the entire composition range. The
Poly(Trimethylene Terephthalate)––The New Generation of Engineering 609
Young’s modulus decreases continuously from around 3,200 MPa for pure PEI to
around 2,200 MPa for pure PTT. The addition of PEI affects the crystallinity of
PTT (decreases from around 27% for neat PTT to around 3% for 25 wt% blend) blend),
but the mechanism of crystal growth is seen to be unaffected. The blends ows a
nds shows
s
synergistic behavior in modulus of elasticity (which is attributed to o a decrease in
y res
$
?$ XJ
?
?
stress of PEI rich blends, and ductile nature.
Krutphun et al. (2008) studied the miscibility, crystallization
llization and optical
opt
op prop-
erties of PTT/PBT blends. The presence of a single andd compositional
composition dependant
op P
Tg by using DSC indicates miscibility of the blends ds in th
the molten
molte state. Fitting the
experimental Tg
"
$
C ic
1.37 indicating the miscibility. The crystallinity
tion of PBT and the banded spherulite structure
ity of PTT decreases
llinity d
cture of PTT becomes
ases with the addi-
omess more open
op as the
or m
amount of PBT in the blends is increased.
reased.
d.
th de
19.10 PTT COMPOSITES AND
ND NANOCOMPOSITES
NANOC
NANO POSITES
Table 13 summarizes selected PTT-based micro
cted PTT-ba
PTT-b croo and nanocomposites
nanocom
na and the
reason(s) behind the preparation
paration of
o the
t composites.
mposi
os
Au ca
PTT composites
mpos The
he preparation oof composites Ref.
TT
T composites
PTT
e
pl
Impr
Improvement of the thermo-me-
PTT/chopped glass fiber
PTT/cho ber ch
h
chanical properties (Mohanty et al.,
(CGF)
CGF) Improvement in tensile strength, im- 2003)
Ap
PTT nanocomposites
s
prepared by using twin screw extruder at temperature of 230–2455oC and at the
y res
screw speed of 100 rpm. The composite pellets obtained were subjected jected to injec-
inje
inj
o
tion moulding at the barrel temperature of 235 C and mouldd temperature mperature at 35oC.
With the addition of CGF, the tensile strength of the bio-based PTT increases
from around 50 MPa to around 110 MPa (for composites tes with 40 wt%
w of CGF).
op P
V%L%X
'V
V L%
L%
MPa (PTT/40 wt% CGF). Composites with 40 wt% CG CGF shows veryve high heat
C ic
o
distortion temperature (HDT) at around 220 20 C. The impaimpact strength
ength sho
sh
shows an in-
crease from 30 J m–1 for PTT to around 90 J m–1 for the th PTT/CGF.
/CGF.
GF. Morpholo
Morph
Morphological
or m
analysis of the tensile fractured samples indicate good dispersion
mples indicates ersion of the CGF
C in
the matrix of PTT. Thus, all these se results lead to the conclusion
clusion that the PP-g-MA
th de
-
lization
ation PTT. The DSC
tion rate of PT
P C results obtained
ob
o for the increase in rate of crystal-
e
<
J_#$
<
pl
The PTT-based
he PT
PTT-ba nanocomposites have been studied extensively by different
d nanocompos
groups. Run et al. (2007)
groups 07) investigated
2007) inv the rheology, meling behavior, and crys-
Ap
s
shows a strong diffraction peak at 2T = 4.10o corresponding to the he (001)
01) plane.
y res
This shows exfoliation of the clay in the PTT matrix and the TEM M images also
aal
#J
Tg shifts from ~ 60 C for neat Po
PTT to
~80oC for the PTT/clay nanocomposites. Similarly a ten fold increase increas in E’ values
is also observed which is explained on the basis of improvement
ovement in ccrystallization
op P
capacity of the PTT matrix.
After the discovery of carbon nanotube (CNT) by Ijima IIj (1991),
991 extensive
C ic
works have been devoted in extracting thee optimum
(2009) studied PTT/MWCNT composites.
propertiess of the
ptimum prop
es. The hydroxyl
osites. hydr
hyd
he CNTs.
C
functionalized
ctionalize (MW-
(
Wu
or m
CNT-OH) behaves as anchoring sites or the PTT grafted
tes for ed with aci (PTT-
th acrylic acid
g-AA) (compare to Scheme 1).. The functionalization
functiona on off MWCNT imp improves the
th de
PTT/MW
PTT/MWCNT PTT-g-AA/MWCNT-OH
pl
MWCNT oor
MWCN
MWCNT-O
MWCNT-OH
(wt%) Initiall decomposi-
decom
dec
Ap
(IDT)
tion temperature Tg (oC) Tm (oC) Tg (oC) Tm (oC)
(oC)
(IDT) (oC)
y res
Physical Chemistry of Macromolecules: Macro to Nanoscales
s
Ap
pl
e
A
Poly(Trimethylene Terephthalate)––The New Generation of Engineering
re to prepare the
SCHEME 1 The synthesis and modification of PTT and MWCNT and the procedure t blends as proposed
roposed
oposed by W
Wu et al. (2009)
py re
(adapted from Wu and co-workers).
613
ss
614 Physical Chemistry of Macromolecules: Macro to Nanoscales
19.11 CONCLUSION
The PTT has not attained much attention from the industrialists as well as from fr
the academicians before 2000 due to high production cost of PTT. The discovery overy
of relatively cheap methods for the synthesis of propane diol by bioengineer engineer--
bioengineer-
s
ing route has reduced the production cost of PTT markedly and nd expedites
pedites the
y res
commercialization process. The PTT crystal has triclinic unit it cell,
l, a big zigzag
zig
conformation along the c-axis which is suggested as the attributingttributing factor of high
deformability of PTT. This accounts for its high tendency dency to form fibers. The
op P
above discussion clearly points to the fact that PTT po possesses
esses comparable
comp proper-
ties of polyesters and nylons. The outstanding properties perti off PTT
propertie PT provide a wide
P
range of options for the manufacturers to produce oduce
duce new m materials.. Thee PTT fibers
ma
C ic
are almost similar to wool and have a much
of fast crystallization and elasticity makes
performance.
uch superior per ance. combination
e. A comb
com
es PTT the bbest optionn for bulk con continu-
or m
ous fibers (BCF) carpet yarn. The BCF CF yarns made
mad of PTT T provide excellent
excelle bulk
excell
resistance, appearance retention, n, elastic recovery
on, rec
reco and strain resilience.
resilience The PTT
resilien
th de
extrusion
xtrusion coatin andd blister
usion coatings, ster packs, moreover
m the ability of PTT to be recycled
ithout sacrificing
without sacrificin
sac the
he properties m makes it a potential candidate for future engi-
pl
applications.
neering aapplic ns.
Ap
KEYWORDS
KEYWO
KEY
ACKNOWLEDGMENT
Some of the experimental works discussed in this chapter were supported by Da
Dana
Pembudayaan Penyelidikan (RAGS) 2012 (600-RMI/RAGS 5/3 (14/2012)) 12)) from
upport
ort Initia-
Ministry of Higher Education, Malaysia and Principal Investigator Support Initia-
s
tive (PSI) 2013 (600-RMI/DANA 5/3/PSI(26/2013)) from RMI, UiTM. M.
y res
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e
pl
Ap
Physical
hy Chemistry
ry
s
y es
of Macromolecules
o cules
Pr
Macro to Nanoscales
sca
ale
ic
m
Editors
Chin Han Chan, PhD
Chin Hua Chia, PhD
Sabu Thomas, PhD
PHYSICAL CHEMISTRY OF
s
MACROMOLECULES ES
y res
Macro to Nanoscales
op P
C ic
or m
th de
E
Edited
d byy
Au ca
s
Oakville, ON L6L 0A2 Waretown, NJ 08758
Canada USA
y res
©2014 by Apple Academic Press, Inc.
Exclusive worldwide distribution by CRC Press, a member of Taylor & Francis Group
Grou
op P
No claim to original U.S. Government works
Printed in the United States of America on acid-free paper
C ic
International Standard Book Number-13: 978-1-926895-64-2
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(Hardcov
or m
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ht for individua
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ary of Congress
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pl
Library
braryy and Archives
Archi
Arch Canada Cataloguing in Publication
Ap
Physical
Physic chemistry of macromolecules:
cro macro to nanoscales/edited by Chin Han Chan, Chin
Hua
Hu Chia, and Sabu Thomas.
Includes bibliographical references and index.
ISBN 978-1-926895-64-2 (bound)
1. Macromolecules. I. Chan, Chin Han, editor of compilation II. Chia, Chin Hua, editor
of compilation III. Thomas, Sabu, editor of compilation
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ABOUT THE EDITORS
s
y res
Chin Han Chan, PhD
Chin Han Chan is a registered chemist with research interests terests in physical
physic proper-
phy
ties of polymer blends. She has been elected as council member memb of tthe Malaysian
op P
Institute of Chemistry and she has been appointed nted as the Chair
Ch of the Polymer
Chai
Committee of the Institute of Materials, Malaysia. alaysia. Afte earning
laysia. After g hher doctorate
C ic
from Universiti Sains Malaysia (University
semicrystalline polymer blends, she spent
ity of Science, M Malaysia)
ysia) inn the
nt one year ffor herr postdoctorate
th field of
ostdoctora on o re-
or m
active blends of themoplastic elastomers.
stomers. Currently, she
mers. Curren
Curre he is an associate pprofes-
sor at the Faculty of Applied Sciences of Universiti
Un iti Teknolgi
eknolgi MARA
MA (MARA
th de
20 invited lectures
tures international
es for int conferences. She has been one of the editors
onal conferenc
conference
of Malaysian
sian JJournal
laysian rna of Chemistry,
urnal mistry,, Berita
hemistry Beri IKM – Chemistry in Malaysia, and
Berit
booksks published by
oks b Royalyal Society
ciety of Chemistry
C entitled Natural Rubber Materi-
e
She peer-reviews
peer-revie a few
peer-re international journals on polymer science. Her research
ew internat
interest is devoted too modified
modif
mo natural rubber-based thermoplastic elastomers,
Ap
biodegradable
biodegr polyester/polyether
/ blends, and solid polymer electrolytes
Chin
C Hua Chia, PhD
Chin Hua Chia is currently an Associate Professor in the Materials Science Pro-
gramme, School of Applied Physics, Universiti Kebangsaan Malaysia (UKM)
(also known as National University of Malaysia). He obtained his PhD in 2007
in Materials Science (UKM, Malaysia). His core research interests include de-
veloping polymer nanocomposites, bio-polymers, magnetic nanomaterials, bio-
adsorbents for wastewater treatment, etc. He has published more than 50 research
vi About the Editors
s
Sabu Thomas, PhD
y res
Sabu Thomas is the Director of the School of Chemical Sciences, s, Mahatma Gan-
nces,
dhi University, Kottayam, India. He is also a full professor ssor of polymer science
and engineering and the Honorary Director of the Centre entre for Nanoscience
Nano
Nan and
op P
Nanotechnology of the same university. He is a fellow llow of many
man professional
pr bod-
ies. He has authored or co-authored many papers pers in international
inte ti peer-reviewed
journals in the area of polymer processing. He has organized
organiz several
organize eral international
in
int
C ic
conferences and has more than 420 publications,
lications, bbooks and
ions, 11 bo nd two
wo patents
pate to his
patent
or m
credit. He has been involved in a number er of books both as author
mber uthor and editor.
edito
ed He
is a reviewer to many international and has received
onal journals an ceived many aw awards for
th de
his excellent work in polymerr processing. His h-index
rocessing. H
Hi list as the 5th
ndex is 42. He is listed
li
position in the list of Mostt Productive
ductive Researchers
R
Re hers
rs in India, in 2008.
200
Au ca
A
e
pl
Ap
CONTENTS
s
List of Contributors ....................................................................................
......................
............... ix
y res
List of Abbreviations ..................................................................................
.....................
.............. xi
Preface .......................................................................................................xv
.............
.....................
Part 1
op P
Physical Chemistry of Macromolecules
acrom ecules
ecule
C ic
1. Introduction ................................................................................................
......................
............... ..........
... 3
Hans-Werner Kammer
or m
2. Molecular Mass of Macromolecules
lecules
les and Its Distribution
ribution
tion...............
.......................
........... 9
Hans-Werner Kammer
th de
3. Macromolecules in Solution
olution
ion...........
.....................................................................
........... ......................
............................ 25
Hans-Werner Kammerr
4. Characterization
ion off Polymers
Polymer
Polyme by Flowing
Flowin
win Behavior
Behavi ............................. 47
Au ca
Hans-Werner Kammer
mm
5. Transitions
ions
ns in Polymers
Polyme ............................................................................
......................
............ 61
A
Hans-Werner
-W nerr Kammer
Kamme
Ka
6. Crystallization
Crystalliz
ystalli ionon and Melting
ting of Polymers
Poly ................................................ 93
e
Hans-Werner
Hans-Wern Kammer
K mer
7. Polymers
Polym in Non-Equilibrium
Non-Equilibriu
on-Equilibriu ............................................................... 119
pl
Hans-Werner
Han
Hans-We Kammer
mer
8. Liquid-Crystalline
Liq
Liqu ine
ne Order
O in Polymers ................................................. 163
Ap
Hans-Werner
H Kammer
9. Surface Tension of Polymer Blends and Random Copolymers .......... 181
Hans-Werner Kammer
10. Macromolecules in the Condensed State .............................................. 201
Hans-Werner Kammer
11. Molecular Characterization of Synthetic Polymers by Means of
Liquid Chromatography ........................................................................ 221
Dušan Berek
viii Contents
s
Advanced Polymeric Materials––Macro to Nanoscales
cales
es
y res
13. Preparation of Chitin-Based Nano-Fibrous and Composite mpositesite
Materials Using Ionic Liquids ...............................................................
...................... 367
Jun-Ichi Kadokawa
op P
14. Fire-Resist Bio-Based Polyurethane for Structural uc al Foam F
Application ..............................................................................................
............
...... .. 385
Khairiah Haji Badri and Amamer Musbah Omran
mran Redwan
C ic
15. Graft Copolymers of Guar Gum vs Alginate––D
Alginate––Drug
Delivery Applications and Implications
plications ................................................
ations.......
... ...........................
................ 423
or m
Animesh Ghosh and Tin Wui Wongg
16. Thermal Properties of Polyhydroxyalkanoates
Polyhydroxyal
olyhydroxy ates ...................................
......................
.................. 441
th de
With Environmental
ental Friendly
nmental Friend Palm Oil-Based
lm Oil
Oil-B sedd Resins
Resi
R ....................... 475
Siang Yin Lee and Seng Neon
Neo Gan
N
18. Miscibility,
ility,
y, Thermal Properties
erties
es and Ion Conductivity
C of
A
Poly(Ethylene
ene Oxide)
y(E hylene Oxi and
nd Polyacrylate
Polyacrylat ................................................ 503
Lai Har Si
Sim, Siti
Sim iti Rozana
na Bt.
t. Abd. Karim,
Karim
Kar and Chin Han Chan
e
19.
9. Poly(Trimethylene
Poly(Trim
Poly(Trimeth ne Terephthala
Terephthalate)––The New Generation of
Engineering
Enginee
Engineerin Thermoplastic
hermoplastic Polyester................................................... 573
pl
Sarathchandran
Sarathcha
ara n C, Chin Han Chan, Siti Rozana Bt. Abd. Karim, and Sabu Thomas
Index ........................................................................................................
Ind
Inde .....
... 619
Ap