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Molecular Weight Determination of Polyethylene Terephthalate

Chapter · August 2015

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

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 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-
plastic polymer used for daily household objects to
sophisticated engineering applications. Due to its
significant water and moisture resistance, it is widely
used in making plastic bottles for soft drinks. PET
is also known by other trade names such as Mylar,
Decron, Terylene, Recron, and Lavsan. It is a high-
crystalline melting temperature (260°C) polymer.
It also possesses significant mechanical strength,
toughness, and thermal resistance up to 150–175°C.
Its chemical, hydrolytic, and solvent resistance con-
stitutes some of the qualities due to the stiffness of
the polymer chains of the PET. Due to its outstanding
crease resistance and good abrasion resistance, this
polymer can be treated with cross-linking resins to im-
part permanent wash and wear properties [1–3]. PET
can be blended with cellulosic fibers such as cotton to
give “better feeling.” The main applications of PET
are wearing apparel, curtains, upholstery, threads, tire
cord filaments, industrial fibers, and fabric for indus-
trial filtration [4]. The outstanding barrier properties
of PET result in film-making applications such as
photographic, magnetic, X-ray films or tapes, metal-
ized films, and also in electrical insulation. This poly-
mer also finds an application in enginnering plastic,
where it replaces steel, aluminum, and other metals in
the manufacture of precision moldings for electrical
and electronic devices, domestic and office applianc-
es, and automobile parts. PET is also reinforced with
glass fiber or compounded with silicones, graphite, or
Teflon® to improve strength and rigidity [1].
The PET polymer is usually prepared by melt-
phase polymerization with an intrinsic viscosity in
the range of 0.5–0.7 dL/g (Table 8.1). A solid state
polymerization must be carried out to obtain higher
intrinsic viscosity polymer. This process involves
Table 8.1 The Intrinsic Viscosity Range of Different Grades of PET [5]
PET Type
Textile grade
Technical and tire cord grade
Film grade (for biaxially oriented film)
Film grade (for thermoforming sheet grade)
Water bottles (flat)
Carbonated soft drink grade
Monofilament, engineering plastic
Figure 8.1  Chemical structure of PET.
heating a solid polymer of low molecular weight,
where the melt phase is below its melting point and
above its glass transition temperature (Tg) [1].
PET is a semicrystalline polymer with excel-
lent chemical resistance, melt mobility, and spin-
nability [1]. This polymer contains repeating units
of terephthalic acid and ethylene glycol, as shown
in Figure 8.1. Each unit of the polymer possesses a
molecular weight of ∼200 Da. When prepared from
the reaction of terephthalic acid and ethylene glycol,
a water molecule is liberated during the reaction,
which must be removed under high temperature and
vacuum. The presence of water in the molten state of
the polymer rapidly depolymerizes the structure. A
textile grade polymer will have an average number of
100 repeat units per polymeric chain with an average
molecular weight of ∼20,000 Da [1].
8.2  Determination of PET
Molecular Weight
Determination of PET molecular weight is very
important, because it can affect the mechanical prop-
erties of a solid polymer indirectly by influencing the
physical state. Fundamental characteristics of a poly-
mer are its chemical structure and molecular weight
distribution. The latter gives the average molecular
size and explains how regular are the sizes of the
polymeric chains. The distribution of molecular size
depends on the synthesis of the polymer. The fun-
damental characteristics of a polymer determine all
the other properties of the polymer, such as cohesive
Intrinsic Viscosity (dL/g)
0.40–0.70
0.72–0.98
0.60–0.70
0.70–1.00
0.70–0.78
0.78–0.85
1.00–2.00
8:  Molecular Weight Determination of Polyethylene Terephthalate 145
forces, packaging density, potential crystallinity, and
molecular mobility of the polymer; this means the to-
tal behavior of the polymer depends on the molecular
weight distribution [6,7].
Measurements of average degree of polymeriza-
tion are done either by molten viscosity (by measur-
ing the pressure drop through a calibrated orifice) or
viscosity of a diluted polymer in an appropriate sol-
vent [8]. The latter method is also known as intrinsic
viscosity of a polymer in the solvent. The molecular
weights of PET polymers used for various purposes
are important and affect their mechanical and physi-
cal properties significantly. If molecular weight is
too low, the transition temperatures and mechanical
properties generally are also too low for the polymer
material to have any useful commercial applications.
A useful polymer must have transition temperatures
above room temperature, and it should have mechan-
ical properties sufficient to bear design loads. Differ-
ent grades of PET require different molecular weight
requirements. Moreover, the molecular weight of
PET polymers significantly affects its degradation
and thereby its environmental fate [9].
Viscosity depends on the molecular weight distri-
bution of a polymer. Satisfactory correlation between
viscosity of diluted solutions and molecular weight
with different chain length has been observed. How-
ever, the limiting factor of this type of correlation is
the presence of branched chains in the polymer struc-
ture. It is, therefore, possible for linear polymers, but
not for branched polymers, to observe an empiric
relation with viscosity. Determination of molecular
weight is possible through measuring viscosities in
diluted solutions. Correlations have also been ob-
served between the viscosity of a certain polymer
and its hydrodynamic volume or its average chain
dimension, such as radius of gyration and the dis-
tance between chain extremities [9,10]. However,
these empiric relations depend on parameters such
as solvent and temperature that alter the molecular
size of polymers in solution. Therefore, solvents and
temperatures must be specified in conjunction with
viscosity data for a correct identification [9].
8.2.1  Intrinsic Viscosity Method
The determination of the intrinsic viscosity of
PET is extremely important, because safer process-
ing conditions can be established by getting this
information in advance. Intrinsic viscosity of PET
samples can be easily determined either in solution
or from melt-flow index (MFI) measurements. The
viscosity determination of a diluted solution can
provide information about the molecular character-
istics of certain polymers. When the viscosity data
are correlated with other molecular parameters, it is
possible to predict certain properties related to the
molecular structure [10].
Solution viscosity measurement of the PET sam-
ples is conducted to determine the intrinsic viscosity.
Viscosity is calculated following standard methods
ASTM D 4603 or 2857 [11]. The difference between
these two methods is that ASTM D 4603 allows the de-
termination of the intrinsic viscosity of a PET sample
with a single concentration, as opposed to successive
dilutions of the original solution with ASTM D 2857.
ASTM D 4603 is only applicable at 30°C, whereas
the ASTM D 2857 method can be used at other tem-
peratures. Usually an Ubbelohde-type viscometer is
used in the determination of intrinsic viscosities of
the polymer solution (Figure 8.2). A solvent mixture
composed of 60/40 phenol/1,1,2,2- tetrachloroethane
is used to prepare the PET solutions. After complete
solubilization, solutions are filtered and the exact
concentration of the resultant solutions is determined
by evaporation of a known volume of the solution
[9]. It is possible to calculate the relative (ηrel), inher-
ent (ηinh), reduced (ηred), and intrinsic [η] viscosities
from the known concentrations of polymer solutions
by the following equations:
ηrel = t / t 0 (8.1)
ηinh = ln ηrel/c (8.2)
ηred = (ηrel − 1) / c (8.3)
[η ] = 0.25ηrel − 1 + 3ln ηrel/c (8.4)
where t, flow time of polymer solution (s); to, flow
time of pure solvent mixture (s); c, polymer solution
concentration (g/dL).
The Billmeyer equation (Equation (8.4)), allows
the determination of the intrinsic viscosity of a poly-
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
obtain the intrinsic viscosity at 25°C, which will then
be related to the constants “K” and “a” of the Mark–
Houwink equation (Equation (8.6)). These constant
values can be obtained from the literature [13,14].
The inherent (ηinh) and reduced (ηred) viscosities can
be obtained from Equations (8.2) and (8.3) using
the ASTM D 2857 method. A plot of “ηinh” versus
“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
of the extrapolation of both plots to zero concentra-
tion [10]. The extrapolated curves will cross each
other at the same point on the viscosity axis in the
intrinsic viscosity, which can be seen in Figure 8.3.
After measuring the flow timings of diluted
polymer solution, another way to use the Schulz–
Blaschke equation (Equation (8.5)) to calculate the
intrinsic viscosity is as follows [15]
(ηrel − 1) / c = [η ] + K SB [η ](ηrel − 1)
After measuring the flow times of all PET samples
at 25 and 30°C using the ASTM D 4603 and ASTM
D 2857 methods and calculation of intrinsic viscosity,
it is possible to use these data to obtain the Schulz–
Blaschke constant (KSB). It is possible to calculate KSB
at 25 and 30°C using the relative viscosity (ηrel) of a
PET solution of known concentration to obtain the in-
trinsic viscosity (η). This equation can be applied to
calculate the intrinsic viscosity of an unknown PET
sample by just measuring the flow at a specified con-
(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
for Determination of Average Molecular Weights
NIR GPC
Time (h) Method Method % Difference
3 343 467 26.6
6 1396 1348 −3.6
10 1694 1967 13.9
14 4569 3844 −18.9
18 6520 6043 −7.9
Adapted from ref. [21].
(average molecular weight vs. absorbance) of poly-
ester samples. The calibration curve is best described
as a third-order mathematical model determined
using the shareware program Kurv+ for Windows
software. There is good agreement in the molecular
weight determination using both NIR and gel perme-
ation chromatography (GPC) methods. Less agree-
ment has been observed at higher average molecular
weight than at lower average molecular weight. The
difference in the average molecular weights by the
NIR and GPC methods is agreed to within 50–400
units (Table 8.5). This is an advantageous method, as
one can control the reaction by checking the peaks in
NIR with respect to target molecular weights [21].
8.2.5  End Group Determination
of PET by NMR Spectroscopy
Proton nuclear magnetic resonance (1H-NMR)
spectroscopy for end group determination of polyes-
ters has been reported in the literature. Shit and Maiti
carried out a study on the 1H-NMR spectra of very
low molecular weight PET in dimethyl sulfoxide-d6.
The authors were able to assign and quantify signals
due to alcohol end groups and derivatized acid end
groups [22]. Pétiaud et al. conducted a more detailed
analysis of oligo PET using both 1H- and 13C-NMR
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
on analysis of the 1H-NMR of PET in CF3COOD/
CDCl3 at room temperature. All signals in the re-
gion 4.1–4.6 ppm were attributed to end groups of
aliphatic origin [24–26]. Application of this tech-
nique in the estimation of the molecular weights
of commercial PET samples provided an apparent
Mn of 4000. This Mn value was substantially lower
than that expected on the basis of the known intrin-
sic viscosities and was inconsistent with GPC data.
The discrepancy may be attributed to overlap of the
signals at 4.65 and 4.16 ppm due to the methylene
protons of the end group aliphatic chains of ethylene
glycol with those of the methylene protons of dieth-
ylene glycol units that are present in the backbone
of the polymer. The signals between ethylene gly-
col and diethylene glycol can be resolved by using
higher field NMR (500 MHz). However, according
to the authors, the end group analysis by 1H-NMR
with CF3COOD/CDC13 as the solvent is not a reli-
able method for the direct determination of the mo-
lecular weight of PET [25].
The use of 13C-NMR for the end group deter-
mination of PET offers greater advantage. The use
of HFIP–CDC13 solvent mixtures for 13C-NMR
analysis avoids the problems found with the use of
CF3COOD–CDC13 solvent. Hexafluoro-2-propanol
(HFIP) in combination with CDC13 is a good sol-
vent mixture for PET and has been successfully
used for GPC analysis of PET. Chemical shifts with
HFIP–CDC13 are similar to those observed with CF-
COOD–CDC13 (Table 8.6). One should note that
3
this solvent should not be used for recording the
1
H-NMR studies, as the signal due to HFIP meth-
ane proton overlaps with PET methylene protons. A
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-
peared in the NMR spectrum. The end group anal-
ysis of high molecular weight PET polymers was
also performed with this technique providing longer
acquisition times (greater than 20 h by 500 MHz
NMR) to obtain a spectrum for quantitative deter-
mination [25]. Recently, the authors reported the use
of 1H-NMR analysis for PET fiber comparison of
seven fiber pairs, with HFIP–CDC13 mixture used
[27]. Differences in spectra analysis were found;
these differences include peak shifts, different peak
splitting, and the appearance of new peaks as shown
in Figure 8.5.
8.2.6  Determination of Molecular
Weight by Gel Permeation
Chromatography
GPC is a size exclusion chromatography that sep-
arates analytes based on their molecular weight. It
was first developed in 1955 by Lathe and Ruthven.
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
rapid and reliable technique compared to other tech-
niques in determining the molecular weights of the
polymers. The GPC instrument is most commonly
calibrated with polystyrene standard samples with a
very narrow molecular weight [28]. During the de-
velopmental stages of GPC, the elution volume of
a polymer was not merely a function of molecular
weight [29]. Benoit et al. showed that chemically and
structurally different polymers yield a common cali-
bration curve if M[η] is plotted as a function of η,
where [η] is the intrinsic viscosity [28]. M[η] can be
used as a universal calibration parameter for linear,
flexible molecules and also for star-shaped branched
molecules [30]. This was experimentally confirmed
for many linear polymers at the time [31,32]. Later,
Pannell showed that there might be a deviation for
branched polymers [33].
GPC was a practical method for the determination
of molecular weights of PET fibers even with 1 mg
sample size. This method is reproducible and accu-
rate for microgram analysis and can be used for com-
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.
This method, although simple, may have significant
impact on the characterization of PET fibers. GPC
systems are affordable and may have a strong impact
on PET fiber comparison in fields such as industry
and forensic science.
8.2.6.1  Methods for Obtaining Molecular
Weight from GPC
8.2.6.1.1  An Iterative Algorithm Method
This was developed independently by Weiss and
Cohn-Ginsberg for their studies [31]. The hydrody-
namic volume Ji of the species i is given by:
J i = [η ]i M i
Making use of the Mark–Houwink relationship:
[η ] = K M a
and the intrinsic viscosity for the whole polymer:
[η ] = ∑ Wi [η ]i
where Wi, is the weight fraction and [η]i is the intrin-
sic viscosity of the species i, one can show that:
[η ] = K 1/( a +l ) ∑ Wi J ia /( a +1)
The value of Ji is determined from the universal
calibration curve, and Wi is obtained from the GPC
trace. Although “K” and “a” are unknown in Equa-
tion (8.13), their values may be readily approximated
by computer techniques, since the limits of one of
the parameters, “a,” is known, that is, 0.5 ≤ a ≤ 1.0.
An iterative algorithm for use with a digital com-
puter was written to converge rapidly on the best
estimates of “K” and “a” by examining intrinsic vis-
cosity and GPC data for several samples. A compari-
son of calculated Equation (8.4) and [η] observed
values allows the best estimates of “K” and “a” to be
obtained after three or four iterations. After the esti-
mation of “K” and “a” the molecular weight of the
samples can be calculated from the relation:
M W = K − (1/ a +1) ∑ Wi J i1/( a +1) (8.14)
To simplify, the molecular weight calculation will
be reported as shown in the Equation (8.14), whereas
all the equations from (8.10) to (8.14) must be em-
ployed to obtain molecular weight [26].
8.2.6.2  Simplified Molecular
Weight Method
Coll and Gilding [32] used the Mark–Houwink
equation and the Ptitsyn–Eizner equation to show:
log M 2 = (1 / (1 + a2 )) log[ K1 f ( ε 2 ) / K 2 f (ε1 )]
+ (1 + a1 /1 + a2 ) log M1 (8.15)
where subscripts 1 and 2 refer to the terms in the
Mark–Houwink equation for polystyrene and the
polymer of interest, respectively.
Funt and Hornof simplified the previous equation
by assuming that al ≈ a2 for many polymers dissolves
in thermodynamically good solvents [34]. Equation
(8.15) is reduced to form:
(8.10)
M 2 = J / [η ]2 (8.16)
where J is interpolated from the universal calibration
(8.11) curve (Figure 8.6), once M1 has been established by
GPC measurements. This analysis enables one to es-
timate rapidly the molecular weight of a sample with-
(8.12) out the use of sophisticated computer techniques.
8.2.6.3  Dawkins Method
This method is based on the unperturbed dimension
(8.13)
of a polymer, which was reported by Dawkins [35,36].
152 Poly(Ethylene Terephthalate) Based Blends, Composites and Nanocomposites
Figure 8.6  Log–log plot of hydrodynamic volume as
a function of polystyrene molecular weight (Pw) [28].
The molecular weight of a sample is estimated from
the following relation:
Log ( M w )2 = log[(〈r02 〉 / M1 ) / [(〈r02 〉 / M 2 )]
+ (log M w )1
where the subscripts 1 and 2 refer to polystyrene
and the sample of interest, respectively. The quantity
((r02)/M) is the unperturbed dimension of the macro-
molecule, and values are available in the literature for
a wide variety of polymers [37–39].
8.2.6.4  Mobile Phase for the
Determination of Molecular Weight
of PET by GPC
Tetrahydrofuran, chloroform, and toluene are
most common solvents for the determination of mo-
lecular weights of common polymers such as poly-
styrene. Construction of a calibration curve from the
GPC system using these solvents as mobile phase is
straightforward, due to polystyrene standard ease
solubility [40]. However, PET is an unmanageable
polymer for the determination of molecular weights
by GPC. Initially, m-cresol was used as mobile phase
for the elution of PET using GPC; due to the vis-
cous nature of this solvent, higher column tempera-
ture (125°C) must be used, which leads to polymer
degradation. Other solvents used in GPC for the PET
are a mixture of nitrobenzene and tetrachloroethane
at room temperature; degradation of PET was not ob-
served for several months [40]. However, difficulties
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
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-
roform. The direct calibration method is employed
for the determination of weight average molecular
weights of the PET samples. Mn and Mw are measured
with the developed method. They are also calculated
(8.17) to show the viscosity average molecular weight (Mv)
of the PET samples under the study. The Mn and Mw
values obtained using the GPC method are in good
agreement with Mv, since the latter lies in between
the Mn and Mw. The results obtained were presented
in Table 8.7. This method allows determination of the
molecular weights of PET samples without affecting
the cross-linked polystyrene gel columns [43].
Size-exclusion chromatography (SEC) has been
used for the determination of molecular weights of
five PET samples, which are dissolved in eluted in
HFIP at 25°C. Mn and Mw and polydispersity are cal-
culated and again recalculated by taking into account
differences between the poly(methyl methacrylate)
standards in relation to those of the PET samples.
It was observed in one study that all PET samples
show a similar degree of polydispersity, which means
having the same molecular weights (Table 8.8). The
Table 8.7  Molecular Weights of PET Samples
Measured by the Sreenivasan and Nair Method [43]
Dispersity
Sample Mn Mw Mv (Mw/Mn)
A 24,000 58,175 54,767 2.42
B 25,000 54,669 40,553 2.19
C 24,009 62,147 56,009 2.59
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
these fibers [27]. This method has provided high re-
producible values for the tested fiber samples.
In another study the authors used the same meth-
od to determine the molecular weights of various
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
and 8.11. The samples were dissolved in HFIP and
analyzed in the HFIP:chloroform 2:98 v/v using
GPC. These results show GPC can be applied with as
low concentration as 1 mg/mL of PET samples for the
determination of molecular weights. These results
strongly highlight the efficiency of the developed
method for PET molecular weight differentiation for
comparison studies in fields such as forensics as well
as industrial production quality tracking and control.
8.3  Applications of PET
PET is one of the most important polymers engi-
neered in last 20 years. As the literature shows, it has
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-
cations and most commonly used for making liquid
containers (bottles). PET polymers have a desired
tensile strength, chemical resistance, clarity, ease of
fabrication, can impart different colors, and have re-
cyclability and thermal stability. Table 8.9 summa-
rizes the main properties of PET [44].
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
ethylene group and the presence of the p-phenylene
group. This chain inflexibility significantly affects
PET structure-related properties such as thermal
transitions [45].
8.3.1  In Biomedical Research
PET has been used in medical devices for more
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-
cess devices [46]. In another form of PET, the fibers
are used in a variety of devices such as a substructure
for heart valves, endovascular devices, sutures, and
other applications. Among the available PET fibers,
HT PET (high-tenacity polyester) fibers are consid-
ered next-generation device applications. HT PET
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-
taining high strength and flexibility [47,48].
In biomedical research, physicians and engineers
are looking for miniaturization in every field, like
delivery systems, transcatheter applications, nano
devices, and artificial organ replacements (venous
transplant, valves, etc.). Therefore, medical device
companies are looking for smaller and stronger fi-
bers. HT PET may be customized and tailor-made
to meet strict regulatory specifications, without com-
promising performance [49].
8.3.2  The Advantages
of HT PET [50]
8.3.2.1  Strength and Flexibility
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
enhanced strength enables device thickness to be re-
duced while maintaining strength and flexibility.
8.3.2.2  Medical-Grade Compatibility
RxFibron HT PET is the first commercially re-
leased, medical-grade, high-tenacity PET on the
market. It enables integration with surrounding tis-
sue, making it ideal for applications such as sutures,
and in endovascular and vascular surgery and ortho-
pedics.
8.3.2.3  Ease of Fabrication
RxFibron HT can be custom-made easily to meet
a variety of device specifications. It exhibits appro-
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
weak points along the structure.
8.3.2.4  Ideal Elongation
With an average elongation of 12, this makes PET
well suited for implantable devices that need to inter-
act with body tissue and therefore maintain durable
flexibility.
PET may be used in orthopedic bandages, plasters,
surgical gowns, masks, drapes, blankets, protective
clothing, etc. Commercially available biodegradable
devices are employed in sutures, orthopedic fixation
devices, dental implants, ligature clips, tissue staples,
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
of the use of PET in biomedical research are shown
in Table 8.10.
8.3.3  PET Clay Nanocomposites
Polymer–clay nanocomposites are synthesized via
melt intercalation, common solvent mixing, or in situ
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
process of melt mixing, the layered silicate is mixed
with a molten polymer matrix. If the silicate surfaces
are sufficiently compatible with the chosen polymer,
then the polymer can enter the interlayer space and
form either an intercalated or an exfoliated nanocom-
posite. Exfoliation or a high level of intercalation is
important in producing a polymer–clay nanocom-
posite; with such separation of individual clay sheets
high aspect ratios are obtained with the inorganic
reinforcing materials [98,99]. The synthesis of PET
clay nanocomposites has not been as successful as
other polymers. Takekoshi et al. prepared polyester
clay nanocomposites via in situ polymerization with
quaternary ammonium salt-modified clay and cyclic
PET oligomers [100]. They observed good nanoparti-
cle dispersion and improved physical properties, such
as improved impact strength and elastic modulus. A
more commercially viable approach with convention-
al polymer processing techniques is melt mixing of
the polyester with an organically modified clay [101].
8.4 Conclusions
PET is one of the most important engineered poly-
mers in human history with a wide variety of applica-
tions in the biomedical, industrial, and food sectors.
Molecular weight is the most important characteristic
for determining the mechanical properties and ability to
fabricate PET materials in different forms for different
applications. In this chapter, the authors have reviewed
in detail all the available methods for molecular weight
quantification of PET polyester with the advantages
of each method as well as its limitations. Among the
reviewed methods, GPC analysis with HFIP–CDCl3
as a mobile phase was found to be a practical method
for PET materials/fiber analysis/comparison with high
certainty at 30 ng of injected PET sample size. More-
over, the GPC tool was found to be the most promis-
ing method for ease of use, reproducibility, accuracy of
analysis, and low detection limit.
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