See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/281343994

Molecular Weight Determination of Polyethylene Terephthalate

Chapter · August 2015

DOI: 10.1016/B978-0-323-31306-3.00008-7

CITATIONS READS

2 8,230

4 authors:

Shady Farah Konda Reddy Kunduru

Massachusetts Institute of Technology The David H. Koch Institute for Integrative … University of Hyderabad
43 PUBLICATIONS   835 CITATIONS    38 PUBLICATIONS   344 CITATIONS   

SEE PROFILE SEE PROFILE

Arijit Basu Abraham J Domb

Massachusetts Institute of Technology Hebrew University of Jerusalem
64 PUBLICATIONS   626 CITATIONS    281 PUBLICATIONS   7,370 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Capsule endoscopy View project

Antimicrobial Nanoparticles & Peritoneal Dialysis View project

All content following this page was uploaded by Shady Farah on 21 February 2018.

The user has requested enhancement of the downloaded file.

 8  Molecular Weight Determination
of Polyethylene Terephthalate

Shady Farah, Konda Reddy Kunduru, Arijit Basu,

and Abraham J. Domb1
Institute of Drug Research, School of Pharmacy-Faculty of Medicine,
Center for Nanoscience & Nanotechnology and The Alex Grass Center for Drug Design
and Synthesis, The Hebrew University of Jerusalem, Jerusalem, Israel

O U T L I N E

8.1 Introduction 144

8.2 Determination of PET Molecular Weight 144
8.2.1 Intrinsic Viscosity Method 145
8.2.1.1 Determination of Intrinsic Viscosity from Melt-Flow Index 147
8.2.2 Determination of Molecular Weight by the Mark–Houwink Equation 147
8.2.3 Determination of Molecular Weight by Carboxyl and Hydroxyl End Group
Assay Methods 148
8.2.4 Average Molecular Weight Determination of Polyesters by NIR Spectroscopy 148
8.2.5 End Group Determination of PET by NMR Spectroscopy 149
8.2.6 Determination of Molecular Weight by Gel Permeation Chromatography 149
8.2.6.1 Methods for Obtaining Molecular Weight from GPC 151
8.2.6.2 Simplified Molecular Weight Method 151
8.2.6.3 Dawkins Method 151
8.2.6.4 Mobile Phase for the Determination of Molecular Weight of PET by GPC 152
8.2.6.5 Examples for Molecular Weight Determination Using GPC 152
8.3 Applications of PET 154
8.3.1 In Biomedical Research 155
8.3.2 The Advantages of HT PET [50] 155
8.3.2.1 Strength and Flexibility 155
8.3.2.2 Medical-Grade Compatibility 155
8.3.2.3 Ease of Fabrication 155
8.3.2.4 Ideal Elongation 159
8.3.3 PET Clay Nanocomposites 159
8.4 Conclusions 161
References 161

1
Formerly of Division of Identification and Forensic Sciences (DIFS), Israel Police, Jerusalem, Israel

Poly(Ethylene Terephthalate) Based Blends, Composites and Nanocomposites. http://dx.doi.org/10.1016/B978-0-323-31306-3.00008-7

Copyright © 2015 Elsevier Inc. All rights reserved. 143
144 Poly(Ethylene Terephthalate) Based Blends, Composites and Nanocomposites

8.1 Introduction
Polyethylene terephthalate (PET) is a polyester
synthesized from terephthalic acid and a diol, com-
monly ethylene glycol. PET is a ubiquitous thermo-
Figure 8.1  Chemical structure of PET.
plastic polymer used for daily household objects to
sophisticated engineering applications. Due to its
significant water and moisture resistance, it is widely heating a solid polymer of low molecular weight,
used in making plastic bottles for soft drinks. PET where the melt phase is below its melting point and
is also known by other trade names such as Mylar, above its glass transition temperature (Tg) [1].
Decron, Terylene, Recron, and Lavsan. It is a high- PET is a semicrystalline polymer with excel-
crystalline melting temperature (260°C) polymer. lent chemical resistance, melt mobility, and spin-
It also possesses significant mechanical strength, nability [1]. This polymer contains repeating units
toughness, and thermal resistance up to 150–175°C. of terephthalic acid and ethylene glycol, as shown
Its chemical, hydrolytic, and solvent resistance con- in Figure 8.1. Each unit of the polymer possesses a
stitutes some of the qualities due to the stiffness of molecular weight of ∼200 Da. When prepared from
the polymer chains of the PET. Due to its outstanding the reaction of terephthalic acid and ethylene glycol,
crease resistance and good abrasion resistance, this a water molecule is liberated during the reaction,
polymer can be treated with cross-linking resins to im- which must be removed under high temperature and
part permanent wash and wear properties [1–3]. PET vacuum. The presence of water in the molten state of
can be blended with cellulosic fibers such as cotton to the polymer rapidly depolymerizes the structure. A
give “better feeling.” The main applications of PET textile grade polymer will have an average number of
are wearing apparel, curtains, upholstery, threads, tire 100 repeat units per polymeric chain with an average
cord filaments, industrial fibers, and fabric for indus- molecular weight of ∼20,000 Da [1].
trial filtration [4]. The outstanding barrier properties
of PET result in film-making applications such as
photographic, magnetic, X-ray films or tapes, metal- 8.2  Determination of PET
ized films, and also in electrical insulation. This poly- Molecular Weight
mer also finds an application in enginnering plastic,
where it replaces steel, aluminum, and other metals in Determination of PET molecular weight is very
the manufacture of precision moldings for electrical important, because it can affect the mechanical prop-
and electronic devices, domestic and office applianc- erties of a solid polymer indirectly by influencing the
es, and automobile parts. PET is also reinforced with physical state. Fundamental characteristics of a poly-
glass fiber or compounded with silicones, graphite, or mer are its chemical structure and molecular weight
Teflon® to improve strength and rigidity [1]. distribution. The latter gives the average molecular
The PET polymer is usually prepared by melt- size and explains how regular are the sizes of the
phase polymerization with an intrinsic viscosity in polymeric chains. The distribution of molecular size
the range of 0.5–0.7 dL/g (Table 8.1). A solid state depends on the synthesis of the polymer. The fun-
polymerization must be carried out to obtain higher damental characteristics of a polymer determine all
intrinsic viscosity polymer. This process involves the other properties of the polymer, such as cohesive

Table 8.1 The Intrinsic Viscosity Range of Different Grades of PET [5]

PET Type Intrinsic Viscosity (dL/g)

Textile grade 0.40–0.70
Technical and tire cord grade 0.72–0.98
Film grade (for biaxially oriented film) 0.60–0.70
Film grade (for thermoforming sheet grade) 0.70–1.00
Water bottles (flat) 0.70–0.78
Carbonated soft drink grade 0.78–0.85
Monofilament, engineering plastic 1.00–2.00
8:  Molecular Weight Determination of Polyethylene Terephthalate 145

forces, packaging density, potential crystallinity, and viscosity determination of a diluted solution can
molecular mobility of the polymer; this means the to- provide information about the molecular character-
tal behavior of the polymer depends on the molecular istics of certain polymers. When the viscosity data
weight distribution [6,7]. are correlated with other molecular parameters, it is
Measurements of average degree of polymeriza- possible to predict certain properties related to the
tion are done either by molten viscosity (by measur- molecular structure [10].
ing the pressure drop through a calibrated orifice) or Solution viscosity measurement of the PET sam-
viscosity of a diluted polymer in an appropriate sol- ples is conducted to determine the intrinsic viscosity.
vent [8]. The latter method is also known as intrinsic Viscosity is calculated following standard methods
viscosity of a polymer in the solvent. The molecular ASTM D 4603 or 2857 [11]. The difference between
weights of PET polymers used for various purposes these two methods is that ASTM D 4603 allows the de-
are important and affect their mechanical and physi- termination of the intrinsic viscosity of a PET sample
cal properties significantly. If molecular weight is with a single concentration, as opposed to successive
too low, the transition temperatures and mechanical dilutions of the original solution with ASTM D 2857.
properties generally are also too low for the polymer ASTM D 4603 is only applicable at 30°C, whereas
material to have any useful commercial applications. the ASTM D 2857 method can be used at other tem-
A useful polymer must have transition temperatures peratures. Usually an Ubbelohde-type viscometer is
above room temperature, and it should have mechan- used in the determination of intrinsic viscosities of
ical properties sufficient to bear design loads. Differ- the polymer solution (Figure 8.2). A solvent mixture
ent grades of PET require different molecular weight composed of 60/40 phenol/1,1,2,2- tetrachloroethane
requirements. Moreover, the molecular weight of is used to prepare the PET solutions. After complete
PET polymers significantly affects its degradation solubilization, solutions are filtered and the exact
and thereby its environmental fate [9]. concentration of the resultant solutions is determined
Viscosity depends on the molecular weight distri- by evaporation of a known volume of the solution
bution of a polymer. Satisfactory correlation between [9]. It is possible to calculate the relative (ηrel), inher-
viscosity of diluted solutions and molecular weight ent (ηinh), reduced (ηred), and intrinsic [η] viscosities
with different chain length has been observed. How- from the known concentrations of polymer solutions
ever, the limiting factor of this type of correlation is by the following equations:
the presence of branched chains in the polymer struc-
ture. It is, therefore, possible for linear polymers, but ηrel = t / t 0 (8.1)
not for branched polymers, to observe an empiric
relation with viscosity. Determination of molecular ηinh = ln ηrel/c (8.2)
weight is possible through measuring viscosities in
diluted solutions. Correlations have also been ob- ηred = (ηrel − 1) / c (8.3)
served between the viscosity of a certain polymer
and its hydrodynamic volume or its average chain [η ] = 0.25ηrel − 1 + 3ln ηrel/c (8.4)
dimension, such as radius of gyration and the dis-
tance between chain extremities [9,10]. However, where t, flow time of polymer solution (s); to, flow
these empiric relations depend on parameters such time of pure solvent mixture (s); c, polymer solution
as solvent and temperature that alter the molecular concentration (g/dL).
size of polymers in solution. Therefore, solvents and The Billmeyer equation (Equation (8.4)), allows
temperatures must be specified in conjunction with the determination of the intrinsic viscosity of a poly-
viscosity data for a correct identification [9]. mer solution at 30°C with a unique concentration
as mentioned in ASTM D 4603 [11]. The ASTM D
2857 method, possible at any temperature, is used to
8.2.1  Intrinsic Viscosity Method obtain the intrinsic viscosity at 25°C, which will then
be related to the constants “K” and “a” of the Mark–
The determination of the intrinsic viscosity of Houwink equation (Equation (8.6)). These constant
PET is extremely important, because safer process- values can be obtained from the literature [13,14].
ing conditions can be established by getting this The inherent (ηinh) and reduced (ηred) viscosities can
information in advance. Intrinsic viscosity of PET be obtained from Equations (8.2) and (8.3) using
samples can be easily determined either in solution the ASTM D 2857 method. A plot of “ηinh” versus
or from melt-flow index (MFI) measurements. The “c” and another of “ηred” versus “c” must be done in
146 Poly(Ethylene Terephthalate) Based Blends, Composites and Nanocomposites

Figure 8.2  Illustrative image for the Ubbelohde viscometer [12].

order to get the intrinsic viscosity at 25°C by means After measuring the flow times of all PET samples
of the extrapolation of both plots to zero concentra- at 25 and 30°C using the ASTM D 4603 and ASTM
tion [10]. The extrapolated curves will cross each D 2857 methods and calculation of intrinsic viscosity,
other at the same point on the viscosity axis in the it is possible to use these data to obtain the Schulz–
intrinsic viscosity, which can be seen in Figure 8.3. Blaschke constant (KSB). It is possible to calculate KSB
After measuring the flow timings of diluted at 25 and 30°C using the relative viscosity (ηrel) of a
polymer solution, another way to use the Schulz– PET solution of known concentration to obtain the in-
Blaschke equation (Equation (8.5)) to calculate the trinsic viscosity (η). This equation can be applied to
intrinsic viscosity is as follows [15] calculate the intrinsic viscosity of an unknown PET
sample by just measuring the flow at a specified con-
(ηrel − 1) / c = [η ] + K SB [η ](ηrel − 1) (8.5) centration. The Schulz–Blaschke equation method, in

Figure 8.3  Plot of viscosity versus concentration for BPET at 30°C [9].
8:  Molecular Weight Determination of Polyethylene Terephthalate 147

Table 8.2 Intrinsic Viscosity of PET Samples [9]

Intrinsic Viscosity (dL/g)

Temperature (°C)
25 30
Sample Method Ia Method IIb Method IIIc Method Ia Method IIb Method IIIc
BPET – 0.80 0.81 0.75 0.73 0.75
RPET – 0.80 0.77 0.75 0.73 0.74
RPET comp – 0.69 0.69 0.67 0.67 0.67
FPET – 0.69 0.67 0.66 0.64 0.64
RYNITE – 0.55 0.54 0.51 0.51 0.51
a
Method I: ASTM D 4603 – Intrinsic viscosity determination by Billmeyer’s equation; applicable only at 30°C.
b
Method II: ASTM D 2857 – Intrinsic viscosity determination by using successive dilutions of the original solution.
c
Method III: Intrinsic viscosity determination from the Schulz–Blaschke equation.

contrast to method ASTM D 4603 that also allows by means of the application of a 2060 g weight. The
the determination of intrinsic viscosity with just one MFI is obtained in gram/10 min, and is correlated
concentration, gives the same information at differing to the internal calibration curve of the equipment to
temperatures of solution as long as the KSB value at obtain the corresponding intrinsic viscosity [9].
the respective temperature is available [9]. The intrinsic viscosity results obtained from MFI
The intrinsic viscosity of PET in solution is deter- are presented in Table 8.3. Results show that the best
mined in triplicate and averaged for each of the five melting time for all PET samples studied is 120 s.
PET samples. The data are presented in Table 8.2. It At 120 s, the intrinsic viscosities of PET samples do
has been observed from the table that the intrinsic not differ much from those obtained by the solution
viscosity values obtained at 25°C from methods II technique at 30°C. At melting times 240 and 360 s a
and III do not differ greatly, except for the recycled decrease in intrinsic viscosities is observed. This is
polyethylene terephthalate (RPET) sample. The due to the degradation of polymers under high tem-
slightly higher difference in this case is due to com- peratures for such longer periods.
position heterogeneities of the recycled bottle flakes.
The difference in intrinsic viscosity results at 30°C is
practically negligible for all the samples evaluated. 8.2.2  Determination of Molecular
The Schulz–Blaschke constants (KSB) were calcu- Weight by the Mark–Houwink
lated using relative and intrinsic viscosities obtained
using both the methods ASTM D 4603 and ASTM D
Equation
2857. The intrinsic viscosities presented in Table 8.2 Viscosity to average molecular weight of a polymer
were calculated by using the KSB values 0.2345 at sample can be calculated using the Mark–Houwink
25°C and 0.3236 at 30°C [9].
Table 8.3  Intrinsic Viscosity of PET Samples
by MFI [9]
8.2.1.1  Determination of Intrinsic
Viscosity from Melt-Flow Index Intrinsic Viscosity (dL/g)
The MFI of PET samples can be determined using Melting Time (s)
the method ASTM D 1238 Standard test method for Sample 120 240 360
flow rates of thermoplastics by extrusion plastometer
BPET 0.77 0.75 0.74
[16]. Melt Indexer Dynisco–Kayeness Polymer Test
Systems model LMI 4004 instrument with a heating RPET 0.74 0.70 0.69
chamber set at 285°C is used for the PET melting RPET comp 0.86 0.80 0.79
timings. After calculating the melting time (120, 240,
FPET 0.66 0.64 0.63
or 360 s, depending on the molecular weight of the
sample), the material is forced through a capillary Rynite 0.89 0.89 0.83
148 Poly(Ethylene Terephthalate) Based Blends, Composites and Nanocomposites

equation (Equation (8.6)) with the help of the calcu- Table 8.4  Determination of Molecular Weights
lated intrinsic viscosities of the polymer solution as by the Mark-Houwink Method [9]
mentioned in the previous section [17].
Sample Mw Mn
[η ] = KM a (8.6) BPET 57,300 37,000
However, to use Equation (8.6), one must know RPET 55,200 35,800
the exact values of “K” and “a,” which are specific RPET comp 45,700 30,000
for fixed conditions of polymer type, solvent, and
temperature. For the condition such as PET, which is FPET 44,700 29,400
solubilized in 60/40 phenol/1,1,2,2-tetrachloroethane Rynite 32,300 21,700
at 25°C, the following relations can be found in the
literature [5,18,19]:
the polymer is immersed in heavy water (D2O), this
η = 3.72 × 10 −4 ( M n )0.73 (8.7) causes these groups of protons to be replaced with
deuterium –OD and –COOD.
η = 4.68 × 10 −4 ( M w )0.68 (8.8) The average molecular weight is calculated using
a series of unfractionated PET samples by carboxyl
To calculate the molecular weights of the PET and hydroxyl end group assay methods [20]. The re-
polymers using the above-mentioned equations, the lation between intrinsic viscosity in a 50:50 ratio of
intrinsic viscosity value used for each sample is the phenol–tetrachloroethane and molecular weight is as
average between the values obtained by ASTM D mentioned below
2857 and the Schulz–Blaschke equation method. The
average intrinsic values for bottle-grade PET (BPET), [η ]dL/g = 2.1 × 10 −4 ( M n )0.82 (8.9)

RPET, RPET Comp, fiber-grade PET (FPET),
and Rynite are 0.805, 0.785, 0.690, 0.680, and
0.545 dL/g, respectively. Weight average and number 8.2.4  Average Molecular Weight
average molecular weights (Mw and Mn, respectively)
of the PET samples presented in the Table 8.4 are
Determination of Polyesters
calculated by the Mark–Houwink method. by NIR Spectroscopy
Average molecular weight is determined during
8.2.3  Determination of Molecular polyester preparation (in-process) by fiber optics near
Weight by Carboxyl and Hydroxyl infrared spectroscopy (NIR) using the UOP Guided
End Group Assay Methods Wave software. The disappearance of the hydroxyl-
ic functionality (1415 nm) from one of the starting
PET is a linear polymer in which end groups are materials is monitored (Figure 8.4). Average molec-
hydroxyl (–OH) and carboxylic acid (–COOH). When ular weight is determined from a calibration curve

Figure 8.4  Repeated NIR scans showing decreasing absorbance of 1415 and 2020 nm overtones. Absorbance
units (AU) versus wavelength (nm). Adapted from Ref. [21].
8:  Molecular Weight Determination of Polyethylene Terephthalate 149

Table 8.5  NIR and GPC Methods Comparison than that expected on the basis of the known intrin-
for Determination of Average Molecular Weights sic viscosities and was inconsistent with GPC data.
The discrepancy may be attributed to overlap of the
NIR GPC
signals at 4.65 and 4.16 ppm due to the methylene
Time (h) Method Method % Difference
protons of the end group aliphatic chains of ethylene
3 343 467 26.6 glycol with those of the methylene protons of dieth-
6 1396 1348 −3.6 ylene glycol units that are present in the backbone
of the polymer. The signals between ethylene gly-
10 1694 1967 13.9
col and diethylene glycol can be resolved by using
14 4569 3844 −18.9 higher field NMR (500 MHz). However, according
18 6520 6043 −7.9 to the authors, the end group analysis by 1H-NMR
with CF3COOD/CDC13 as the solvent is not a reli-
Adapted from ref. [21].
able method for the direct determination of the mo-
lecular weight of PET [25].
(average molecular weight vs. absorbance) of poly- The use of 13C-NMR for the end group deter-
ester samples. The calibration curve is best described mination of PET offers greater advantage. The use
as a third-order mathematical model determined of HFIP–CDC13 solvent mixtures for 13C-NMR
using the shareware program Kurv+ for Windows analysis avoids the problems found with the use of
software. There is good agreement in the molecular CF3COOD–CDC13 solvent. Hexafluoro-2-propanol
weight determination using both NIR and gel perme- (HFIP) in combination with CDC13 is a good sol-
ation chromatography (GPC) methods. Less agree- vent mixture for PET and has been successfully
ment has been observed at higher average molecular used for GPC analysis of PET. Chemical shifts with
weight than at lower average molecular weight. The HFIP–CDC13 are similar to those observed with CF-
difference in the average molecular weights by the COOD–CDC13 (Table 8.6). One should note that
3
NIR and GPC methods is agreed to within 50–400 this solvent should not be used for recording the
units (Table 8.5). This is an advantageous method, as 1
H-NMR studies, as the signal due to HFIP meth-
one can control the reaction by checking the peaks in ane proton overlaps with PET methylene protons. A
NIR with respect to target molecular weights [21]. quantitative 13C-NMR experiment was conducted on
a low molecular weight PET sample (Mn ∼ 3000).
Signals due to the alcohol and acid end groups ap-
8.2.5  End Group Determination peared in the NMR spectrum. The end group anal-
of PET by NMR Spectroscopy ysis of high molecular weight PET polymers was
also performed with this technique providing longer
Proton nuclear magnetic resonance (1H-NMR) acquisition times (greater than 20 h by 500 MHz
spectroscopy for end group determination of polyes- NMR) to obtain a spectrum for quantitative deter-
ters has been reported in the literature. Shit and Maiti mination [25]. Recently, the authors reported the use
carried out a study on the 1H-NMR spectra of very of 1H-NMR analysis for PET fiber comparison of
low molecular weight PET in dimethyl sulfoxide-d6. seven fiber pairs, with HFIP–CDC13 mixture used
The authors were able to assign and quantify signals [27]. Differences in spectra analysis were found;
due to alcohol end groups and derivatized acid end these differences include peak shifts, different peak
groups [22]. Pétiaud et al. conducted a more detailed splitting, and the appearance of new peaks as shown
analysis of oligo PET using both 1H- and 13C-NMR in Figure 8.5.
spectra in dimethyl sulfoxide-d6 at 140°C and pro-
vided assignments for both the aliphatic and aromat-
ic end groups [23]. Pinkus and Hariharan reported
the determination of the aliphatic end groups based 8.2.6  Determination of Molecular
on analysis of the 1H-NMR of PET in CF3COOD/ Weight by Gel Permeation
CDCl3 at room temperature. All signals in the re- Chromatography
gion 4.1–4.6 ppm were attributed to end groups of
aliphatic origin [24–26]. Application of this tech- GPC is a size exclusion chromatography that sep-
nique in the estimation of the molecular weights arates analytes based on their molecular weight. It
of commercial PET samples provided an apparent was first developed in 1955 by Lathe and Ruthven.
Mn of 4000. This Mn value was substantially lower The term GPC was coined by J.C. Moore of Dow
Figure 8.5  (a–c) showing differences in 1H-NMR spectra of PET fiber pair overlays, A2:B2 (spectrums interval:
1–9, 3–3.50, 2.25–2.50 ppm), A4:B4 (spectrums interval: 1–9, 4.50–4.80, 3–3.60 ppm), and A5:B5 (spectrums
interval: 1–9, 3–5, 7.80–8.30 ppm), respectively. Peak shifting and different splitting were found in pair spectra
comparison. 1H-NMR (CDCl3: HFIP mixture, ppm), 2.36 (s, 1H, HFIP), 4.43 (m, 1H, HFIP), 3.12 (d, solvent
mixture), 4.50–4.70 (t, 4H, O=C–O–CH2–CH2–O–C=ONH2), 8.00–8.25 (d, 4H, aromatic benzene ring’s protons).
Adapted from Ref. [27].

Table 8.6 13C-NMR Chemical Shifts of Comonomers and End Groups in PET Derivatives [25]

Chemical Shift (ppm) in Solvents

CF3COOD/CDCl3 HFIP/CDCl3 DMSO−d6
Structures a b a b a b
64.5 – 63.3 – 61.4 –

69.6 65.2 – – 66.7 62.5

67.4 61.3 66.6 60.9 65.1 57.6

65.7 63.6 – – – –

166.7 – 167.7 – 163.4 –

166.7 – 167.7 168.1 163.6 164.6

8:  Molecular Weight Determination of Polyethylene Terephthalate 151

Chemical Company in 1964. GPC is accepted as a The value of Ji is determined from the universal
rapid and reliable technique compared to other tech- calibration curve, and Wi is obtained from the GPC
niques in determining the molecular weights of the trace. Although “K” and “a” are unknown in Equa-
polymers. The GPC instrument is most commonly tion (8.13), their values may be readily approximated
calibrated with polystyrene standard samples with a by computer techniques, since the limits of one of
very narrow molecular weight [28]. During the de- the parameters, “a,” is known, that is, 0.5 ≤ a ≤ 1.0.
velopmental stages of GPC, the elution volume of An iterative algorithm for use with a digital com-
a polymer was not merely a function of molecular puter was written to converge rapidly on the best
weight [29]. Benoit et al. showed that chemically and estimates of “K” and “a” by examining intrinsic vis-
structurally different polymers yield a common cali- cosity and GPC data for several samples. A compari-
bration curve if M[η] is plotted as a function of η, son of calculated Equation (8.4) and [η] observed
where [η] is the intrinsic viscosity [28]. M[η] can be values allows the best estimates of “K” and “a” to be
used as a universal calibration parameter for linear, obtained after three or four iterations. After the esti-
flexible molecules and also for star-shaped branched mation of “K” and “a” the molecular weight of the
molecules [30]. This was experimentally confirmed samples can be calculated from the relation:
for many linear polymers at the time [31,32]. Later,
Pannell showed that there might be a deviation for M W = K − (1/ a +1) ∑ Wi J i1/( a +1) (8.14)

branched polymers [33].
GPC was a practical method for the determination To simplify, the molecular weight calculation will
of molecular weights of PET fibers even with 1 mg be reported as shown in the Equation (8.14), whereas
sample size. This method is reproducible and accu- all the equations from (8.10) to (8.14) must be em-
rate for microgram analysis and can be used for com- ployed to obtain molecular weight [26].
parison if two given PET fibers originate from the
same source. This practical method can be used for
the comparison of any kind of polymers and plastics. 8.2.6.2  Simplified Molecular
This method, although simple, may have significant Weight Method
impact on the characterization of PET fibers. GPC
systems are affordable and may have a strong impact Coll and Gilding [32] used the Mark–Houwink
on PET fiber comparison in fields such as industry equation and the Ptitsyn–Eizner equation to show:
and forensic science.
log M 2 = (1 / (1 + a2 )) log[ K1 f ( ε 2 ) / K 2 f (ε1 )]

+ (1 + a1 /1 + a2 ) log M1 (8.15)
8.2.6.1  Methods for Obtaining Molecular
Weight from GPC where subscripts 1 and 2 refer to the terms in the
Mark–Houwink equation for polystyrene and the
8.2.6.1.1  An Iterative Algorithm Method polymer of interest, respectively.
This was developed independently by Weiss and Funt and Hornof simplified the previous equation
Cohn-Ginsberg for their studies [31]. The hydrody- by assuming that al ≈ a2 for many polymers dissolves
namic volume Ji of the species i is given by: in thermodynamically good solvents [34]. Equation
(8.15) is reduced to form:
J i = [η ]i M i (8.10)
M 2 = J / [η ]2 (8.16)
Making use of the Mark–Houwink relationship:
where J is interpolated from the universal calibration
[η ] = K M a (8.11) curve (Figure 8.6), once M1 has been established by
and the intrinsic viscosity for the whole polymer: GPC measurements. This analysis enables one to es-
timate rapidly the molecular weight of a sample with-
[η ] = ∑ Wi [η ]i (8.12) out the use of sophisticated computer techniques.

where Wi, is the weight fraction and [η]i is the intrin-
sic viscosity of the species i, one can show that: 8.2.6.3  Dawkins Method
This method is based on the unperturbed dimension
[η ] = K 1/( a +l ) ∑ Wi J ia /( a +1) (8.13)
of a polymer, which was reported by Dawkins [35,36].
152 Poly(Ethylene Terephthalate) Based Blends, Composites and Nanocomposites

in preparing the samples were observed. HFIP and

pentafluorophenol as well as their mixtures were
used as the mobile phase in GPC for PET [41]. HFIP
is capable of dissolving the PET at room temperature
and is available commercially. The only disadvan-
tage is that polystyrene standards are not soluble with
this solvent. To overcome this drawback a mixture
of chloroform and HFIP has been used as a mobile
phase [42]. Recently our group studied 14 differ-
ent PET fiber samples using the HFIP:chloroform,
2:98 v/v, as mobile phase for the determination of
their molecular weights [27].

8.2.6.5  Examples for Molecular Weight

Determination Using GPC
Sreenivasan and Nair determined the molecular
weight distribution of PET by GPC using chloroform
Figure 8.6  Log–log plot of hydrodynamic volume as
a function of polystyrene molecular weight (Pw) [28].
as a solvent. In their method, first, PET is dissolved
in 1:1 (v/v) chloroform and phenol at 50°C, and then
1 mL of this solution is diluted four times with chlo-
The molecular weight of a sample is estimated from roform. The direct calibration method is employed
the following relation: for the determination of weight average molecular
Log ( M w )2 = log[(〈r02 〉 / M1 ) / [(〈r02 〉 / M 2 )] weights of the PET samples. Mn and Mw are measured
with the developed method. They are also calculated
+ (log M w )1 (8.17) to show the viscosity average molecular weight (Mv)
of the PET samples under the study. The Mn and Mw
where the subscripts 1 and 2 refer to polystyrene
values obtained using the GPC method are in good
and the sample of interest, respectively. The quantity
agreement with Mv, since the latter lies in between
((r02)/M) is the unperturbed dimension of the macro-
the Mn and Mw. The results obtained were presented
molecule, and values are available in the literature for
in Table 8.7. This method allows determination of the
a wide variety of polymers [37–39].
molecular weights of PET samples without affecting
the cross-linked polystyrene gel columns [43].
8.2.6.4  Mobile Phase for the Size-exclusion chromatography (SEC) has been
Determination of Molecular Weight used for the determination of molecular weights of
five PET samples, which are dissolved in eluted in
of PET by GPC HFIP at 25°C. Mn and Mw and polydispersity are cal-
Tetrahydrofuran, chloroform, and toluene are culated and again recalculated by taking into account
most common solvents for the determination of mo- differences between the poly(methyl methacrylate)
lecular weights of common polymers such as poly- standards in relation to those of the PET samples.
styrene. Construction of a calibration curve from the It was observed in one study that all PET samples
GPC system using these solvents as mobile phase is show a similar degree of polydispersity, which means
straightforward, due to polystyrene standard ease having the same molecular weights (Table 8.8). The
solubility [40]. However, PET is an unmanageable
polymer for the determination of molecular weights Table 8.7  Molecular Weights of PET Samples
by GPC. Initially, m-cresol was used as mobile phase Measured by the Sreenivasan and Nair Method [43]
for the elution of PET using GPC; due to the vis-
cous nature of this solvent, higher column tempera- Dispersity
ture (125°C) must be used, which leads to polymer Sample Mn Mw Mv (Mw/Mn)
degradation. Other solvents used in GPC for the PET A 24,000 58,175 54,767 2.42
are a mixture of nitrobenzene and tetrachloroethane B 25,000 54,669 40,553 2.19
at room temperature; degradation of PET was not ob-
C 24,009 62,147 56,009 2.59
served for several months [40]. However, difficulties
8:  Molecular Weight Determination of Polyethylene Terephthalate 153

Table 8.8  Molecular Weights and Polydispersity among the studied fibers (A1–A7 and B1–B7). Plain
Measured by SEC [9] PET fibers were dissolved in HFIP and analyzed by
GPC using HFIP:chloroform 2:98 v/v as eluent. De-
Sample Mw Mn Mw/Mn
tection limit of the method was checked by analyzing
BPET 49,500 20,100 2.46 the samples with concentration as low as 1 mg/mL.
RPET 40,600 18,900 2.15 A measurable peak was observed with this concen-
tration, as shown in Figures 8.7 and 8.8. Similar
RPET comp 34,600 17,800 1.94
results were obtained for all the tested fibers with
FPET 33,700 17,600 1.91 reproducibility. GPC analysis of PET fibers success-
Rynite 28,400 12,800 2.22 fully discriminated the differences between the fiber
pairs; otherwise, they were not compared using other
most interesting feature of the PET fibers is that even analytical methods. The calculated Mw, Mn, and Mp
small variations in molecular weights can cause con- (molecular weight at the highest point of the peak)
siderable differences in PET properties [9,40]. are given in Figure 8.9 for each fiber sample. All the
GPC analysis of 14 PET fibers was compared PET fibers were discriminated from each other in
in our recent study. This showed the discrimination their calculated molecular weights, so any of these

Figure 8.7  GPC chromatograms of PET fibers with varied concentrations (1–1000 mg/mL) [27].

Figure 8.8  GPC analysis of diluted fiber polymer sample for the molecular weight determination. Fibers were
analyzed by GPC using UV detector at 254 nm, mobile phase 2% v/v HFIP in chloroform at a flow rate of 1 mL/
min and 30 mL injection volume of 1 mg/mL fiber solution [27].
154 Poly(Ethylene Terephthalate) Based Blends, Composites and Nanocomposites

Figure 8.9  Mn, Mp, and Mw of 14 PET fiber samples analyzed by GPC [27].

Mn, Mw, or Mp can be used in the discrimination of determination of molecular weights. These results
these fibers [27]. This method has provided high re- strongly highlight the efficiency of the developed
producible values for the tested fiber samples. method for PET molecular weight differentiation for
In another study the authors used the same meth- comparison studies in fields such as forensics as well
od to determine the molecular weights of various as industrial production quality tracking and control.
PET samples from five batches of Coca-Cola bot-
tles and from the Reference Collection of Synthetic
Fibers (1987). Results are presented in Figures 8.10 8.3  Applications of PET
and 8.11. The samples were dissolved in HFIP and
analyzed in the HFIP:chloroform 2:98 v/v using PET is one of the most important polymers engi-
GPC. These results show GPC can be applied with as neered in last 20 years. As the literature shows, it has
low concentration as 1 mg/mL of PET samples for the experienced rapid growth in its use. It is regarded as

Figure 8.10  Mn, Mp, and Mw of PET samples from five batches of Coca-Cola bottles analyzed by GPC.
8:  Molecular Weight Determination of Polyethylene Terephthalate 155

Figure 8.11  Mn, Mp, and Mw of PET samples from Reference Collection of Synthetic Fibers (1987) analyzed
by GPC.

the best material (the gold standard) for many appli- delivery systems, transcatheter applications, nano
cations and most commonly used for making liquid devices, and artificial organ replacements (venous
containers (bottles). PET polymers have a desired transplant, valves, etc.). Therefore, medical device
tensile strength, chemical resistance, clarity, ease of companies are looking for smaller and stronger fi-
fabrication, can impart different colors, and have re- bers. HT PET may be customized and tailor-made
cyclability and thermal stability. Table 8.9 summa- to meet strict regulatory specifications, without com-
rizes the main properties of PET [44]. promising performance [49].
The PET chain is considered to be stiff above the
Tg unlike many other polymers. The low flexibility
of the PET chain is a result of the nature of the short 8.3.2  The Advantages
ethylene group and the presence of the p-phenylene of HT PET [50]
group. This chain inflexibility significantly affects
PET structure-related properties such as thermal 8.3.2.1  Strength and Flexibility
transitions [45].
HT PET has tenacity >6.5 N/Tex, twice the
strength of standard PET, allowing device manu-
facturers to use smaller yarn for manufacture. This
8.3.1  In Biomedical Research enhanced strength enables device thickness to be re-
PET has been used in medical devices for more duced while maintaining strength and flexibility.
than 50 years. Currently it is used as implantable su-
tures, surgical mesh, vascular grafts, sewing cuffs for
heart valves, and components for percutaneous ac- 8.3.2.2  Medical-Grade Compatibility
cess devices [46]. In another form of PET, the fibers RxFibron HT PET is the first commercially re-
are used in a variety of devices such as a substructure leased, medical-grade, high-tenacity PET on the
for heart valves, endovascular devices, sutures, and market. It enables integration with surrounding tis-
other applications. Among the available PET fibers, sue, making it ideal for applications such as sutures,
HT PET (high-tenacity polyester) fibers are consid- and in endovascular and vascular surgery and ortho-
ered next-generation device applications. HT PET pedics.
has more than double the strength of standard PET
with less bulk density. It has been possible to manu-
facture devices by reducing thickness and size, main- 8.3.2.3  Ease of Fabrication
taining high strength and flexibility [47,48]. RxFibron HT can be custom-made easily to meet
In biomedical research, physicians and engineers a variety of device specifications. It exhibits appro-
are looking for miniaturization in every field, like priate thermal melt properties that allow engineers to
156 Poly(Ethylene Terephthalate) Based Blends, Composites and Nanocomposites

Table 8.9 Overview of Materials for PET Properties [44]

Physical Properties
Density 1.25–1.91 g/cm3
1.10–1.20 g/cm3
@Temperature 285–285°C
Apparent bulk density 0.830–0.950 g/cm3
Water absorption 0.050–0.80%
Moisture absorption at equilibrium 0.20–0.30%
Water absorption at saturation 0.40–0.50%
Particle size 2500–3500 mm
Water vapor transmission 0.490–6.00 g/m2/day
Oxygen transmission 5.10–23.0 cm3-mm/m2-24 h-atm
Oxygen transmission rate 2.00–20.0 cm3/m2/day
Viscosity test 62–86 cm3/g
Maximum moisture content 0.35–0.40
Thickness 200–1200 mm
Linear mold shrinkage 0.0010–0.020 cm/cm
0.010–0.013 cm/cm
@Temperature 150–150°C
0.010–0.013 cm/cm
@Time 900–900 s
Linear mold shrinkage, transverse 0.0020–0.011 cm/cm
0.0010–0.010 cm/cm
@Temperature 150–150°C
0.0010–0.010 cm/cm
@Time 900–900 s
Mechanical Properties
Hardness, Rockwell M 80–96
Hardness, Rockwell R 105–117
Hardness, Shore D 79–81
Ball indentation hardness 160–170 MPa
Tensile strength, ultimate 22.0–155 MPa
Film tensile strength at yield, MD 55.0–260 MPa
Film tensile strength at yield, TD 53.0–265 MPa
Tensile strength, yield 47.0–90.0 MPa
Film elongation at break, MD 40–600%
Film elongation at break, TD 100–600%
Film elongation at yield, MD 4.0–6.0%
Film elongation at yield, TD 4.0–6.0%
Elongation at break 1.5–600%
Elongation at yield 3.5–5.0%
Modulus of elasticity 1.83–5.20 GPa
Flexural yield strength 60.0–240 MPa
Flexural modulus 1.90–13.3 GPa
8:  Molecular Weight Determination of Polyethylene Terephthalate 157

Table 8.9 Overview of Materials for PET Properties  (cont.)

Mechanical Properties
Compressive yield strength 20.0–103 MPa
Izod impact, notched 0.139–100 J/cm
0.270–0.630 J/cm
@Temperature −40.0 to −40.0°C
Izod impact, unnotched 2.67 J/cm–NB
NB–NB
@Temperature −40.0 to −30.0°C
Izod impact, notched (ISO) 2.00–8.10 kJ/m2
3.10–4.20 kJ/m2
@Temperature –40.0 to −40.0°C
Izod impact, unnotched (ISO) NB
160–181 kJ/m2
@Temperature –40.0 to −40.0°C
Charpy impact, unnotched 3.00 J/cm2–NB
NB–NB
@Temperature –30.0 to −30.0°C
Charpy impact, notched 0.200–1.40 J/cm2
0.270–0.500 J/cm2
@Temperature –30.0 to −30.0°C
Puncture energy 12.0–41.0 J
0.800–24.0 J
@Temperature −40.0 to −40.0°C
0.800–24.0 J
@Thickness 2.50–3.20 mm
Coefficient of friction 0.18–0.30
Coefficient of friction, static 0.19–0.40
Tear strength, total 15.0–120 N
Tear strength 0.265–59.0 kN/m
Elmendorf tear strength, MD 3.14–4.00 g/mm
Elmendorf tear strength, TD 3.24–5.20 g/mm
Dart drop 1.08–2.00 g/mm
Taber abrasion, mg/1000 cycles 15–40
Film tensile strength at break, MD 13.8–60.0 MPa
Film tensile strength at break, TD 39.0–48.0 MPa
Electrical Properties
Electrical resistivity 5.00e + 6 to 1.00e + 18 ohm-cm
1.00e + 11 to 1.00e + 12 ohm-cm
@Temperature 150–150°C
Surface resistance 1.00e + 13 to 1.00e + 16 ohm
≥ 1.00e + 12 ohm
@Temperature 150–150°C
Dielectric constant 2.4–3.7
3.6–3.6w
@Temperature 150–150°C
3.6–3.6
@Frequency 50.0–50.0 Hz
(Continued)
158 Poly(Ethylene Terephthalate) Based Blends, Composites and Nanocomposites

Table 8.9 Overview of Materials for PET Properties  (cont.)

Electrical Properties
Dielectric strength 15.7–510 kV/mm
135–200 kV/mm
@Temperature 150–150°C
135–200 kV/mm
@Frequency 50–50 Hz
Dissipation factor 0.0010–0.025
0.0048–0.0048
@Temperature 150–150°C
0.0048–0.0048
@Frequency 50–50 Hz
Dielectric loss index 0.0010–0.014
Arc resistance 80–181 s
Comparative tracking index 175–600 V
Thermal Properties
CTE, linear 25.0–92.0 mm/m-°C
CTE, linear, transverse to flow 48.0–80.0 mm/m-°C
Specific heat capacity 1.00–1.20 J/g-°C
1.21336–2.30 J/g-°C
@Temperature 60–280°C
Thermal conductivity 0.190–0.290 W/m-K
Melting point 200–260°C
Maximum service temperature, air 100–225°C
Deflection temperature at 0.46 MPa (66 psi) 66.0–245°C
Deflection temperature at 1.8 MPa (264 psi) 60.0–240°C
Vicat softening point 74.0–85.0°C
Minimum service temperature, air −20.0°C
Glass transition temp, Tg 70.0–78.0°C
Flammability, UL94 HB - V-0
Oxygen index 22–25%
Optical Properties
Haze 0.30–40%
Gloss 108–166%
Transmission, visible 67–99%
Processing Properties
Processing temperature 90.0–293°C
Melt temperature 120–295°C
Mold temperature 10.0–163°C
Drying temperature 70.0–160°C
Moisture content 0.10–0.40%
Injection pressure 68.9–120 MPa
8:  Molecular Weight Determination of Polyethylene Terephthalate 159

melt yarn for fabrication, thus avoiding gluing and devices, dental implants, ligature clips, tissue staples,
weak points along the structure. skin covering devices, stents, dialysis media, and
drug-delivery devices. It is also being evaluated as a
material for tissue engineering [51]. A few examples
8.3.2.4  Ideal Elongation of the use of PET in biomedical research are shown
With an average elongation of 12, this makes PET in Table 8.10.
well suited for implantable devices that need to inter-
act with body tissue and therefore maintain durable
flexibility. 8.3.3  PET Clay Nanocomposites
PET may be used in orthopedic bandages, plasters,
surgical gowns, masks, drapes, blankets, protective Polymer–clay nanocomposites are synthesized via
clothing, etc. Commercially available biodegradable melt intercalation, common solvent mixing, or in situ
devices are employed in sutures, orthopedic fixation polymerization. These are one of the most widely

Table 8.10 Examples of Recently Reported Biomedical Applications of PET

Applications Remarks References

Artificial ligament and Biocompatible and nonabsorbable artificial ligaments made from [52,53]
osteointegration modified PET show significant abrasion and mechanical robust-
ness. Coating with biocompatible materials enhances the accept-
ability.
PET-based fibrous 1. Highly porous fibrous mats are important for drug delivery, [54]
mats for biomedical wound dressing, implants, tissue engineering scaffolds, etc.
applications PET-based fibrous mats are reported with desired mechanical
properties.
2. PET surface rendered biocompatible by plasma processing im- [55]
mobilization of collagen and different other proteins.
3. Self-polymerizable dopamine was grafted on a layer of PET [56]
sheet, followed by covalently grafting lysine (Lys) to improve
hemocompatibility and antibiofouling property.
Protein adsorption on PET substrates for possible use in [57]
biomedical applications.
PET-based grafts 1. Heparin-surfaced, thrombus-resistant PET-based grafts [58]
reported. The outer surface for these grafts coated with collagen
immobilized on the graft for better biocompatibility.
2. Gene delivery from PET grafts coated with polyethylene imine [59]
meant to deliver SiRNA from aortic smooth muscles.
3. Nonwoven fibrous vascular graft with properties resembling na- [60]
tive vessels has been reported. Vascular cell growth, preserva-
tion of cell phenotype, retention of vasoactive properties, as well
as the effect of gelatin coating on the cellular interaction with the
scaffolds under static and shear stress conditions have been
reported. The nonwoven fibrous scaffolds were made from melt
blown PET fiber.
4. Losi et al. reviewed the current status of synthetic vascular graft [61]
made with PET (Dacron®) and expanded polytetrafluoroethyl-
ene (ePTFE). They emphasize these synthetic grafts may be
successfully used to replace large diameter vessels, but they fail
in small diameters (<6 mm) such as for infragenicular bypasses.
5. Cardiac valves bovine pericardial tissue valve self-expanding [62] Detailed
nitinol frame with polyethylene terephthalate skirt CENTERA® review [63]
(Edwards Lifesciences) 23, 26, and 29 mm.

(Continued)
160 Poly(Ethylene Terephthalate) Based Blends, Composites and Nanocomposites

Table 8.10 Examples of Recently Reported Biomedical Applications of PET  (cont.)

Applications Remarks References

Fibrous PET matrices 1. Carbon nanotube coated with PET matrices to act as scaffold [64]
for tissue engineering for promoting neuronal differentiation in embryonic stem cells.
2. PET membrane grafted with peptides. The grafted peptides [65]
increase cell adhesion, proposed to use endothelialized PET for
the surgery of small-diameter vascular prostheses.
PET-based stents and 1. Initial experience with PET-based stents was not favorable, they [66,67]
balloons elicit immune responses and vessel occlusions.
2. Later hybrid stents based on metallic core and outer PET mesh [68,69]
repurposed PET into stent development with the discovery of
MGuard stent. MGuard stent is now the gold standard in stents
and has undergone many successful clinical trials. They are
called mesh-covered stents.
3. Smarter grafted PET-based stents have also been reported.
(a) Integration of the aortic walls by recruiting host cells.
(b) Heparin conjugated PET-based stents for enhanced biocom- [70–72]
patibility.
(c) Stents meant for in vivo endothelialization that uses PET as [73]
base material.
(d) A surface-modified stent with chondroitin sulfate and epider- [74]
mal growth factor to promote healing after stenting process.
4. Commercially available angioplasty balloons are commonly [75]
made of PET, and catheters can be of polyurethane, polyethyl-
ene, styrene-butadiene rubber, or polystyrene.
Interpenetrating polymer network of poly(acrylamide-co-ethylene [76–78]
glycol) (p(AAm-co-EG)) hydrogel covalently grafted to PET an-
gioplasty balloons to increase surface hydrophilicity and improve
lubricity has been reported. Similar interpenetration and grafting
has also been subsequently observed.
Shape-memory PET 1. Thermoresponsive polypropylene/PET polymer with shape- [79]
memory effect was prepared. The polymer was compatibilized
by maleic anhydride-grafted polyethylene-octene elastomer.
2. PET/polyethylene blended thermoresponsive shape-memory [80]
polymers were synthesized using ethylene-butyl acrylate-glycidyl
methacrylate terpolymer as a reactive compatibilizer.
As a supportive material for two-way behavior shape-memory [81]
polymer actuators.
Implantable medical devices. [82,83]
Medical electronics 1. Silver nanowires coated with transparent PET layer were [84]
prepared.
2. In conductive polymer composites, electrically conductive, [85]
microfibrillar PET/polyethylene (PE) composite (FCMC).
3. Flexible electronic devices based on PET flexible. Metal– [86]
insulator–metal capacitors have been fabricated. The devices
show excellent electrical stability and high mechanical flexibility.
Medical films Films with antimicrobial properties are important for medical [87]
devices, sterile packaging, and sanitization.
Several reports with PET-based films grafted with cationic biocom- [88–91]
patible materials like chitosan, polyethylene imine, PEG amine, etc.
8:  Molecular Weight Determination of Polyethylene Terephthalate 161

explored materials made from PET [92–97]. In the [3] A.J. East, Polyester fibres, in: J.E. McIntyre
process of melt mixing, the layered silicate is mixed (Ed.), Synthetic Fibres, Woodhead Publish-
with a molten polymer matrix. If the silicate surfaces ing, Witney, Oxford, UK, 2005, pp. 95–166
are sufficiently compatible with the chosen polymer, (Chapter 3).
then the polymer can enter the interlayer space and [4] H. Saleh, T. Bayoumi, H. Shatta, Mechanical
form either an intercalated or an exfoliated nanocom- and chemical characterizations of polyester
posite. Exfoliation or a high level of intercalation is modified cement immobilizing nuclear wastes,
important in producing a polymer–clay nanocom- Adv. Chem. Sci. 1 (2012) 12–17.
posite; with such separation of individual clay sheets [5] V.B. Gupta, Z. Bashir, PET fibers, films, and
high aspect ratios are obtained with the inorganic bottles: sections 5–7, in: Handbook of Thermo-
reinforcing materials [98,99]. The synthesis of PET plastic Polyesters, Wiley-VCH, Verlag GmbH &
clay nanocomposites has not been as successful as Co., KGaA, 2005, pp. 362–388.
other polymers. Takekoshi et al. prepared polyester [6] D.W. van Krevelen, K. te Nijenhuis, –Polymer
clay nanocomposites via in situ polymerization with properties, in: D.W. van Krevelen , K. te Nijen-
quaternary ammonium salt-modified clay and cyclic huis (Eds.), Properties of Polymers, fourth ed.,
PET oligomers [100]. They observed good nanoparti- Elsevier, Amsterdam, 2009, pp. 3–5 (Chapter 1).
cle dispersion and improved physical properties, such [7] N.J. Kim, J.H. Bang, S.W. Choi, E.R. Kim,
as improved impact strength and elastic modulus. A Determination of the molecular weight distri-
more commercially viable approach with convention- butions from rheological properties of visco-
al polymer processing techniques is melt mixing of elastic polymers, J. Ind. Eng. Chem. 2 (1996)
the polyester with an organically modified clay [101]. 97–105.
[8] J.E. McIntyre, Synthetic Fibres: Nylon, Polyes-
ter, Acrylic, Polyolefin, Elsevier, Witney, Oxford,
8.4 Conclusions UK, 2004.
[9] N. Sanches, M. Dias, E. Pacheco, Comparative
PET is one of the most important engineered poly-
techniques for molecular weight evaluation of
mers in human history with a wide variety of applica-
poly (ethylene terephthalate) (PET), Polym.
tions in the biomedical, industrial, and food sectors.
Test. 24 (2005) 688–693.
Molecular weight is the most important characteristic
[10] ASTM D 2857: Standard Test Method for Dilute
for determining the mechanical properties and ability to
Solution Viscosity of Polymers, in: American
fabricate PET materials in different forms for different
Society for Testing and Materials, Philadelphia,
applications. In this chapter, the authors have reviewed
1994.
in detail all the available methods for molecular weight
[11] ASTM D 4603: Standard Test Method for De-
quantification of PET polyester with the advantages
termining Inherent Viscosity of Poly(Ethylene
of each method as well as its limitations. Among the
Terephthalate) (PET), in: American Society for
reviewed methods, GPC analysis with HFIP–CDCl3
Testing and Materials, Philadelphia, 1994.
as a mobile phase was found to be a practical method
[12] Anatomy of a Viscometer, in Machinery Lubri-
for PET materials/fiber analysis/comparison with high
cation. http://www.machinerylubrication.com/
certainty at 30 ng of injected PET sample size. More-
Read/29451/anatomy-of-viscometer, 2015.
over, the GPC tool was found to be the most promis-
[13] Z. Roslaniec, D. Pietkiewicz, Synthesis and char-
ing method for ease of use, reproducibility, accuracy of
acteristics of polyester-based thermoplastic elas-
analysis, and low detection limit.
tomers: chemical aspects: sections 6–7, Hand-
book of Thermoplastic Polyesters, Wiley-VCH,
References Verlag GmbH & Co., KGaA, 2005, pp. 629–658.
[14] V.B. Gupta, Z. Bashir, PET fibers, films, and bot-
[1] S. Venkatachalam, S.G. Nayak, J.V. Labde, P.R. tles: sections 1–4.13, in: Handbook of Thermo-
Gharal, K. Rao, A.K. Kelkar, Degradation and plastic Polyesters, Wiley-VCH, Verlag GmbH
Recyclability of Poly(Ethylene Terephthalate), & Co., KGaA, Weinheim, Germany, 2005,
Polyester, in: Hosam El-Din M. Saleh (Ed.) pp. 317–361.
vol. 107, 2012. [15] H.-G. Elias, Macromolecules, vol. 1. Plenum
[2] G. Reese, Polyesters, Fibers, Encyclopedia of Press, New York, 1984.
Polymer Science and Technology, John Wiley [16] ASTM D 1238: Standard Test Method for
& Sons, Inc, New Jersey, USA, 2002. Flow Rates of Thermoplastics by Extrusion
162 Poly(Ethylene Terephthalate) Based Blends, Composites and Nanocomposites

Plastometer, in: American Society for Testing [31] A.R. Weiss, E. Cohn-Ginsberg, A note on the
and Materials, Philadelphia, 1994. universal calibration curve for gel permeation
[17] M. Kurata, Y. Tsunashima, Viscosity–molecular chromatography, J. Polym. Sci. Part B 7 (1969)
weight relationships and unperturbed dimen- 379–381.
sions of linear chain molecules, Wiley Database [32] H. Coll, D.K. Gilding, Universal calibration in
of Polymer Properties, 2003. GPC: a study of polystyrene, poly-a-methylsty-
[18] S. Jabarin, Crystallization kinetics of polyeth- rene, and polypropylene, J. Polym. Sci. Part A 8
ylene terephthalate. I. Isothermal crystallization (1970) 89–103.
from the melt, J. Appl. Polym. Sci. 34 (1987) [33] J. Pannell, Gel permeation chromatography:
85–96. the behaviour of polystyrenes with long-chain
[19] S. Jabarin, Crystallization kinetics of polyethyl- branching, Polymer 13 (1972) 277–282.
ene terephthalate. II. Dynamic crystallization of [34] B. Funt, V. Hornof, An approach to a simpli-
PET, J. Appl. Polym. Sci. 34 (1987) 97–102. fied universal calibration for gel permeation
[20] A. Conix, On the molecular weight determina- chromatography, J. Appl. Polym. Sci. 15 (1971)
tion of poly (ethylene terephthalate), Die Mak- 2439–2445.
romol. Chemie 26 (1958) 226–235. [35] J. Dawkins, Gel permeation chromatography
[21] S.J. Robbins, W.D. Mockel, C.J. Lyons, Average of polymers: use of unperturbed dimensions for
molecular weight determination of a polyester by calibration, J. Macromol. Sci. Part B 2 (1968)
NIR spectroscopy, ISA Trans. 33 (1994) 377–380. 623–639.
[22] S.C. Shit, S. Maiti, Application of NMR spec- [36] J. Dawkins, P. Holdsworth, A. Keller, Reversible
troscopy in molecular weight determination of long period variations with temperature in sin-
polymers, Eur. Polym. J. 22 (1986) 1001–1008. gle crystals of branch-containing polyethylenes,
[23] R. Pétiaud, H. Waton, Q.-T. Pham, A 1H and Die Makromol. Chem. 118 (1968) 361–374.
13C NMR study of the products from direct [37] J. Dawkins, J. Maddock, Gel permeation chroma-
polyesterification of ethylene glycol and tere- tography: calibration procedures for linear poly-
phthalic acid, Polymer 33 (1992) 3155–3161. ethylene, Eur. Polym. J. 7 (1971) 1537–1548.
[24] R. Hariharan, A.G. Pinkus, Useful NMR solvent [38] J. Dawkins, J. Maddock, A. Nevin, Gel perme-
mixture for polyesters: trifluoroacetic acid-d/ ation chromatography: calibration procedures
chloroform-d, Polym. Bull. 30 (1993) 91–95. for chains containing p-phenylene units, Eur.
[25] B. Fox, G. Moad, G. Van Diepen, I. Willing, Polym. J. 9 (1973) 327–343.
W.D. Cook, Characterization of poly (ethylene [39] J. Dawkins, Test of polymer size parameters for
terephthalate) and poly (ethylene terephthalate) calibration in gel permeation chromatography,
blends, Polymer 38 (1997) 3035–3043. Eur. Polym. J. 6 (1970) 831–840.
[26] A. Pinkus, R. Hariharan, Poly-3-and [40] S. Mori, Size exclusion chromatography of
4-hydroxymethylbenzoates: future engineering/ poly (ethylene terephthalate) using hexafluoro-
fiber “plastics”?, J. Macromol. Sci. Part C 33 2-propanol as the mobile phase, Anal. Chem. 61
(1993) 259–289. (1989) 1321–1325.
[27] S. Farah, T. Tsach, A. Bentolila, A.J. Domb, [41] S. Berkowitz, Viscosity–molecular weight re-
Morphological, spectral and chromatography lationships for poly (ethylene terephthalate) in
analysis and forensic comparison of PET fibers, hexafluoroisopropanol–pentafluorophenol using
Talanta 123 (2014) 54–62. SEC–LALLS, J. Appl. Polym. Sci. 29 (1984)
[28] A. Spatorico, B. Coulter, Molecular weight de- 4353–4361.
terminations by gel-permeation chromatogra- [42] K. Hibi, A. Wada, S. Mori, Semi-micro size-
phy and viscometry, J. Polym. Sci. Polym. Phys. exclusion chromatography: molecular-weight
Ed. 11 (1973) 1139–1150. measurement of poly (ethylene terephthalate)
[29] L.W. Gamble, Comparison of two rapid tech- and separation of oligomers and prepolymers,
niques for determining the molecular weight Chromatographia 21 (1986) 635–641.
distribution of polymers, Microchem. J. 11 [43] K. Sreenivasan, P.D. Nair, Determination of mo-
(1966) 105–120. lecular weight distribution of polyethylene tere-
[30] E.F. Casassa, Equilibrium distribution of flex- phthalate by gelpermeation chromatography,
ible polymer chains between a macroscopic so- Bull. Mater. Sci. 8 (1986) 527–530.
lution phase and small voids, J. Polym. Sci. Part [44] Overview of Materials for Polyethylene Tere-
B 5 (1967) 773–778. phthalate (PET), Unreinforced, http://www.
8:  Molecular Weight Determination of Polyethylene Terephthalate 163

matweb.com/search/datasheet.aspx?MatGUID and covalent graft of lysine, J. Biomater. Sci.

=a696bdcdff6f41dd98f8eec3599eaa20, 2015. Polym. Ed. 25 (2014) 1619–1628.
[45] C.E. Carraher Jr., Carraher’s Polymer Chem- [57] N. Recek, M. Jaganjac, M. Kolar, L. Milkovic,
istry, Marcel Dekker Inc, New York, USA, M. Mozetič, K. Stana-Kleinschek, A. Vesel,
(2013). Protein adsorption on various plasma-treated
[46] A. Metzger, Polyethylene terephthalate and polyethylene terephthalate substrates, Mole-
the pillar™ palatal implant: its historical usage cules 18 (2013) 12441–12463.
and durability in medical applications, Biomed. [58] B. Al Meslmani, G. Mahmoud, B. Strehlow, E.
Eng. 11 (1976) 301–306. Mohr, T. Leichtweiß, U. Bakowsky, Develop-
[47] H. Yoon, Melt Spinning of High Performance ment of thrombus-resistant and cell compatible
Poly(ethylene Terephthalate) (PET) Multifila- crimped polyethylene terephthalate cardiovas-
ment Yarn via Utilizing a Horizontal Isothermal cular grafts using surface co-immobilized hepa-
Bath (HIB) in the Threadline, North Carolina rin and collagen, Mater. Sci. Eng. C 43 (2014)
State University, 2012. 538–546.
[48] M. Jaffe, P. Chen, E.-W. Choe, T.-S. Chung, S. [59] C.S. Nabzdyk, M.C. Chun, H.S. Oliver-Allen,
Makhija, High performance polymer blends, S.G. Pathan, M.D. Phaneuf, J.-O. You, L.K.
High Performance Polymers, Springer, Berlin, Pradhan-Nabzdyk, F.W. LoGerfo, Gene silenc-
Heidelberg, Germany, 1994, pp. 297–327. ing in human aortic smooth muscle cells induced
[49] L.-Y. Chen, G. Chen, X.-X. Cai, X.-P. Zhu, by PEI–siRNA complexes released from dip-
X.-D. Zhu, Quality control of high tenacity PET coated electrospun poly(ethylene terephthalate)
industrial yarn, Polyester Ind. 2 (2013) 005. grafts, Biomaterials 35 (2014) 3071–3079.
[50] RxFIBRON HT™, http://www.rxfiber.com/ [60] M.J. Moreno, A. Ajji, D. Mohebbi-Kalhori, M.
fibers/rxfibron-ht%C2%A9.aspx, 2013–2014. Rukhlova, A. Hadjizadeh, M.N. Bureau, De-
[51] L.W. McKeen, 3 – Plastics used in medical de- velopment of a compliant and cytocompatible
vices, in: K.M. Ebnesajjad (Ed.), Handbook of micro-fibrous polyethylene terephthalate vascu-
Polymer Applications in Medicine and Medical lar scaffold, J. Biomed. Mater. Res. Part B Appl.
Devices, William Andrew Publishing, Oxford, Biomater. 97B (2011) 201–214.
2014, pp. 21–53 (Chapter 3). [61] T. Al Kayal, D. Maniglio, W. Bonani, P. Losi,
[52] H. Li, S. Chen, Biomedical coatings on poly- C. Migliaresi, G. Soldani, A combined method
ethylene terephthalate artificial ligaments, for bilayered vascular graft fabrication, J. Mater.
J. Biomed. Mater. Res. Part A 103 (2015) Sci. Mater. Med. 26 (2015) 1–5.
839–845. [62] M. Taramasso, A. Pozzoli, A. Latib, G. La Canna,
[53] C. Vaquette, V. Viateau, S. Guérard, F. Anag- A. Colombo, F. Maisano, O. Alfieri, New de-
nostou, M. Manassero, D.G. Castner, V. Migon- vices for TAVI: technologies and initial clini-
ney, The effect of polystyrene sodium sulfonate cal experiences, Nat. Rev. Cardiol. 11 (2014)
grafting on polyethylene terephthalate artificial 157–167.
ligaments on in vitro mineralisation and in vivo [63] E. Brisbois, H. Handa, M. Meyerhoff, Recent
bone tissue integration, Biomaterials 34 (2013) advances in hemocompatible polymers for
7048–7063. biomedical applications, in: F. Puoci (Ed.),
[54] A. Hadjizadeh, A. Ajji, M.N. Bureau, Nano/ Advanced Polymers in Medicine, Springer In-
micro electro-spun polyethylene terephthal- ternational Publishing, AG Switzerland, 2015,
ate fibrous mat preparation and characteriza- pp. 481–511.
tion, J. Mech. Behav. Biomed. Mater. 4 (2011) [64] R. Zang, S.-T. Yang, Multiwalled carbon
340–351. nanotube-coated polyethylene terephthalate fi-
[55] M. Aflori, M. Drobota, D.G. Dimitriu, I. Stoica, brous matrices for enhanced neuronal differen-
B. Simionescu, V. Harabagiu, Collagen immo- tiation of mouse embryonic stem cells, J. Mater.
bilization on polyethylene terephthalate surface Chem. B 1 (2013) 646–653.
after helium plasma treatment, Mater. Sci. Eng. [65] M. Rémy, R. Bareille, V. Rerat, C. Bourget, J.
B 178 (2013) 1303–1310. Marchand-Brynaert, L. Bordenave, Polyethyl-
[56] X. Zhi, P. Li, X. Gan, W. Zhang, T. Shen, J. Yuan, ene terephthalate membrane grafted with pep-
J. Shen, Hemocompatibility and anti-biofouling tidomimetics: endothelial cell compatibility and
property improvement of poly(ethylene tere- retention under shear stress, J. Biomater. Sci.
phthalate) via self-polymerization of dopamine Polym. Ed. 24 (2012) 269–286.
164 Poly(Ethylene Terephthalate) Based Blends, Composites and Nanocomposites

[66] J. Murphy, R. Schwartz, W. Edwards, A. Cam- [76] S. Park, J. Bearinger, E. Lautenschlager, D.

rud, R. Vlietstra, D. Holmes, Percutaneous Castner, K. Healy, Surface modification of poly
polymeric stents in porcine coronary arteries. (ethylene terephthalate) angioplasty balloons
Initial experience with polyethylene terephthal- with a hydrophilic poly (acrylamide-co-ethylene
ate stents, Circulation 86 (1992) 1596–1604. glycol) interpenetrating polymer network coat-
[67] K. Wilczek, I. De Scheerder, K. Wang, E. ing, J. Biomed. Mater. Res. 53 (2000) 568–576.
Verbeken, J. Piessens, Comparison of self- [77] P. Paoprasert, S. Moonrinta, S. Kanokul, Highly
expanding polyethylene terephthalate and efficient interpenetrating polymerization of sty-
metallic stents implanted in porcine iliac ar- rene and 4-vinylpyridine with poly(ethylene
teries, CardioVasc. Interv. Radiol. 19 (1996) terephthalate) using benzoyl peroxide, Polym.
176–180. Int. 63 (2014) 1041–1046.
[68] G.W. Stone, A. Abizaid, S. Silber, J.M. Dizon, [78] A.N. Rashid, K. Tsuru, K. Ishikawa, Effect of
B. Merkely, R.A. Costa, R. Kornowski, A. Abi- calcium–ozone treatment on chemical and bio-
zaid, R. Wojdyła, A. Maehara, O. Dressler, S.J. logical properties of polyethylene terephthal-
Brener, E. Bar, D. Dudek, Prospective, random- ate, J. Biomed. Mater. Res. Part B 103 (2015)
ized, multicenter evaluation of a polyethylene 853–860.
terephthalate micronet mesh–covered stent [79] Y.-Y. Cui, B.-J. Dong, B.-L. Li, S.-C. Li, Proper-
(MGuard) in ST-segment elevation myocardial ties of polypropylene/poly (ethylene terephthal-
infarction: the MASTER Trial, J. Am. Coll. Car- ate) thermostimulative shape memory blends
diol. 60 (2012) 1975–1984. reactively compatibilized by maleic anhydride
[69] F. Figini, A. Colombo, The role of MGuard stent grafted polyethylene-octene elastomer, Int.
in primary coronary angioplasty, Minerva Car- J. Polym. Mater. Polym. Biomater. 62 (2013)
dioangiol. 62 (2014) 29–38. 671–677.
[70] M. Takeuchi, T. Kuratani, S. Miyagawa, Y. Shi- [80] S.-C. Li, L.-N. Lu, W. Zeng, Thermostimulative
rakawa, K. Shimamura, K. Kin, T. Yoshida, Y. shape-memory effect of reactive compatibilized
Arai, T. Hoashi, N. Teramoto, K. Hirakawa, N. high-density polyethylene/poly(ethylene tere-
Kawaguchi, Y. Sawa, Tissue-engineered stent- phthalate) blends by an ethylene–butyl acry-
graft integrates with aortic wall by recruiting late–glycidyl methacrylate terpolymer, J. Appl.
host tissue into graft scaffold, J. Thorac. Cardio- Polym. Sci. 112 (2009) 3341–3346.
vasc. Surg. 148 (2014) 1719–1725. [81] S. Imai, Operating methods for two-way behav-
[71] G.G. Stefanini, M. Taniwaki, S. Windecker, ior shape memory polymer actuators without
Coronary stents: novel developments, Heart 100 using external stress, IEEJ Trans. Electr. Elec-
(2014) 1051–1061. tron. Eng. 9 (2014) 90–96.
[72] T.M. Jeewandara, S.G. Wise, M.K. Ng, Biocom- [82] W. Khan, E. Muntimadugu, M. Jaffe, A. Domb,
patibility of coronary stents, Materials 7 (2014) Implantable medical devices, in: A.J. Domb, W.
769–786. Khan (Eds.), Focal Controlled Drug Delivery,
[73] J. Li, F. Lin, L. Li, J. Li, S. Liu, Surface engineer- Springer, New York, USA, 2014, pp. 33–59.
ing of poly(ethylene terephthalate) for durable [83] M. Ebara, Y. Kotsuchibashi, K. Uto, T. Aoyagi,
hemocompatibility via a surface interpenetrating Y.-J. Kim, R. Narain, N. Idota, J. Hoffman,
network technique, Macromol. Chem. Phys. Shape-memory materials, Smart Biomaterials,
213 (2012) 2120–2129. Springer, Japan, 2014, pp. 285–373.
[74] Y. Wei, Y. Ji, L.-L. Xiao, Q.-K. Lin, J.-P. Xu, [84] Z. Yu, Q. Zhang, L. Li, Q. Chen, X. Niu, J. Liu,
K.-F. Ren, J. Ji, Surface engineering of cardio- Q. Pei, Highly flexible silver nanowire elec-
vascular stent with endothelial cell selectivity trodes for shape-memory polymer light-emit-
for in vivo re-endothelialisation, Biomaterials ting diodes, Adv. Mater. 23 (2011) 664–668.
34 (2013) 2588–2599. [85] K. Dai, Y.-C. Zhang, J.-H. Tang, X. Ji, Z.-M. Li,
[75] C. Charbonneau, J.-C. Ruiz, P. Lequoy, M.-J. Anomalous attenuation and structural origin of
Hébert, G. De Crescenzo, M.R. Wertheimer, positive temperature coefficient (PTC) effect in
S. Lerouge, Chondroitin sulfate and epidermal a carbon black (CB)/poly(ethylene terephthal-
growth factor immobilization after plasma po- ate) (PET)/polyethylene (PE) electrically con-
lymerization: a versatile anti-apoptotic coating ductive microfibrillar polymer composite with
to promote healing around stent grafts, Macro- a preferential CB distribution, J. Appl. Polym.
mol. Biosci. 12 (2012) 812–821. Sci. 125 (2012) E561–E570.
 8:  Molecular Weight Determination of Polyethylene Terephthalate 165

[86] M. Hota, M. Bera, C. Maiti, Flexible metal– ites by polycondensation, High Perform. Polym.
insulator–metal capacitors on polyethylene 19 (2007) 565–580.
terephthalate plastic substrates, Semicond. Sci. [94] H. Ghasemi, P.J. Carreau, M.R. Kamal, S.H.
Technol. 27 (2012) 105001. Tabatabaei, Properties of PET/clay nano-
[87] L. Bastarrachea, S. Dhawan, S.S. Sablani, En- composite films, Polym. Eng. Sci. 52 (2012)
gineering properties of polymeric-based antimi- 420–430.
crobial films for food packaging: a review, Food [95] S. Hayrapetyan, A. Kelarakis, L. Estevez, Q.
Eng. Rev. 3 (2011) 79–93. Lin, K. Dana, Y.-L. Chung, E.P. Giannelis,
[88] C. Corradini, I. Alfieri, A. Cavazza, C. Lantano, Non-toxic poly (ethylene terephthalate)/clay
A. Lorenzi, N. Zucchetto, A. Montenero, Anti- nanocomposites with enhanced barrier proper-
microbial films containing lysozyme for active ties, Polymer 53 (2012) 422–426.
packaging obtained by sol–gel technique, J. [96] M. Farhoodi, S.M. Mousavi, R. Sotudeh-
Food Eng. 119 (2013) 580–587. Gharebagh, Z. Emam-Djomeh, A. Oromiehie,
[89] J.P. Cerisuelo, R. Gavara, P. Hernández-Muñoz, Migration of aluminum and silicon from PET/
Natural antimicrobial–containing EVOH coat- clay nanocomposite bottles into acidic food
ings on PP and PET films: functional and active simulant, Packag. Technol. Sci. 27 (2014)
property characterization, Packag. Technol. Sci. 161–168.
27 (2014) 901–920. [97] A. Ghanbari, M.-C. Heuzey, P.J. Carreau,
[90] M. Lago, R. Sendón, A.R.-B. de Quirós, A. M.-T. Ton-That, Morphological and rheological
Sanches-Silva, H. Costa, D. Sánchez-Machado, properties of PET/clay nanocomposites, Rheol.
H.S. Valdez, I. Angulo, G. Aurrekoetxea, E. Tor- Acta 52 (2013) 59–74.
rieri, Preparation and characterization of antimi- [98] A. Sanchez-Solis, A. Garcia-Rejon, O. Mane-
crobial films based on chitosan for active food ro, Production of nanocomposites of PET-
packaging applications, Food Bioprocess Tech- montmorillonite clay by an extrusion process,
nol. 7 (2014) 2932–2941. Macromol. Symp. (2003) 281–292.
[91] J. Lei, L. Yang, Y. Zhan, Y. Wang, T. Ye, Y. Li, H. [99] G. Guan, C. Li, D. Zhang, Y. Jin, The effects of
Deng, B. Li, Plasma treated polyethylene tere- metallic derivatives released from montmoril-
phthalate/polypropylene films assembled with lonite on the thermal stability of poly(ethylene
chitosan and various preservatives for antimi- terephthalate)/montmorillonite nanocom-
crobial food packaging, Colloids Surf. B Bioin- posites, J. Appl. Polym. Sci. 101 (2006)
terfaces 114 (2014) 60–66. 1692–1699.
[92] G.D. Barber, B.H. Calhoun, R.B. Moore, Poly [100] Y. Wang, J. Gao, Y. Ma, U.S. Agarwal, Study
(ethylene terephthalate) ionomer based clay on mechanical properties, thermal stability and
nanocomposites produced via melt extrusion, crystallization behavior of PET/MMT nano-
Polymer 46 (2005) 6706–6714. composites, Comp. Part B 37 (2006) 399–407.
[93] D. Pospiech, A. Korwitz, H. Komber, D. Voigt, [101] R. Sharma, H. Joshi, P. Jain, Short review on
D. Jehnichen, J. Müller, A. Janke, T. Hoffmann, the crystallization behavior of PET/clay nano-
B. Kretzschmar, In situ synthesis of poly (ethyl- composites, J. Chem. Eng. Mater. Sci. 2 (2011)
ene terephthalate)/layered silicate nanocompos- 39–43.

View publication stats