Journal of Polymer Research (2021) 28: 475

https://doi.org/10.1007/s10965-021-02824-3

ORIGINAL PAPER

Oxygen barrier films of ­scCO2‑assisted thermoplastic starch/poly (vinyl

alcohol) blends
Nian‑qi Cheng1 · Ya‑qiong Huang1 · Dan‑dan Dai1 · Jen‑taut Yeh1 

Received: 18 July 2021 / Accepted: 5 November 2021 / Published online: 24 November 2021
© The Polymer Society, Taipei 2021

Abstract
Renewable thermoplastic starch (TPS) was modified by poly (vinyl alcohol) (PVA) with varying degrees of polymerization
­ PSxPVAyz or s­ cCO2TPSxPVAyz fully biodegradable blends. The T
(DPs) or s­ cCO2-assisted processing to prepare T ­ PSxPVAyz
y
(or ­scCO2TPSxPVA z) films showed the smallest free volume characteristics and oxygen transmission rates (OTRs), as their
PVA loadings approached an optimum value. The smallest free volume characteristics and OTRs evaluated for each optimal
­TPSxPVAyz (or ­scCO2TPSxPVAyz) films reduced noticeably as their DPs reduced from 2400 to 300. Considerably smaller
OTRs and free volume characteristics were acquired for ­scCO2TPSxPVAyz films than those of corresponding ­TPSxPVAyz
films prepared without the assistance of s­ cCO2. An essential result is that the OTR of the optimal s­ cCO2TPSxPVAyz film
with a moisture content of 4wt% was merely 4.6 ­cm3/m2∙day∙atm. This OTR is as good as that of the polyvinylidene chloride
oxygen barrier packaging. Dynamic mechanical relaxations and WAXD characterizations revealed that TPS and PVA are
miscible, as PVA loadings were ≤ the optimum values. The enhanced oxygen barrier resistance and reduced free volume
characteristics for optimal ­TPSxPVAyz and ­scCO2TPSxPVAyz films are partly ascribed to the strengthened molecular interac-
tions between O–H groups of TPS and PVA, as they were processed with the assistance of s­ cCO2, optimum PVA loadings
or diminished DPs.

Keywords  Thermoplastic starch · Poly (vinyl alcohol) · Supercritical carbon dioxide · Oxygen barrier · Free volume
characteristics

Introduction
The disposal of petroleum-based waste plastics has become
a serious contamination problem to the environment for the
last two decades, because these waste plastics aren’t renewa-
ble or biodegradable materials [1–7]. Laurent and coauthors
reported that ~ 1.2 to ~ 2.4 million tons of disposed plastics
were entering the oceans each year from rivers [8]. More
than half of these waste plastics have densities less than the
Nian-qi Cheng and Ya-qiong Huang the authors are co-first
authors.
* Jen‑taut Yeh
jyeh@mail.ntust.edu.tw
1 based materials have been reported in several investigations
Hubei Collaborative Innovation Center for Advanced
Organic Chemical Materials Ministry of Education, Key
Laboratory for the Green Preparation and Application
of Functional Materials, Hubei Key Laboratory of Polymeric
Materials, Faculty of Materials Science and Engineering,
Hubei University, Wuhan, China
sea water, and they are floating with the oceanic currents as
great garbage patches in oceans until unlikely degradation
into small microplastics for tens of years [8]. Up to the year
of 2019, more than 60 countries have introduced bans or fees
to cut the waste plastics [9], and application of sustainable
or biodegradable plastics has been clearly emphasized. The
annual worldwide demand for sustainable plastics rapidly
surged to 2.11 million tons in 2019 [10], because of the bans
or fees introduced by the government authorities. Among
these sustainable polymers, starch has been considered one
of the most promising materials for packaging applications
because of its attractive combination of low cost, renewabil-
ity, and good oxygen barrier performance [11].
The oxygen and water vapor transmission rates (OTR
and WVTR) for starch- or thermoplastic starch (TPS)-
[12–38]. The OTR values measured at 20 ℃/ ~ 50% rela-
tive humidity (RH) for wheat starch films with a thickness
of ~ 50 and ~ 100 μm have been reported as 60.3 and 16.7
­cm3/m2∙day∙atm [14, 15], respectively. Similar low OTR

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of ~ 37.4 ­cm3/m2∙day∙atm at 20 ℃ and 50% RH has been
reported for the potato starch film (~ 50 μm) in a recent
study [16]. In contrast, cassava starch film having a thick-
ness of ~ 43 μm showed a relatively high OTR of ~ 74.2 ­cm3/
m2∙day∙atm at 23 ℃/50% RH [17]. While the OTR acquired
for mung bean starch (MBS) films (~ 70 μm) measured at
23 °C and 50% RH has been reported as low as ~ 11.4 c­ m3/
m2∙day∙atm more recently [18], which is comparable to
polyvinylidene chloride oxygen barrier plastics. Compared
to these starch films, maize amylopectin or potato amylose
films (~ 50 μm) showed even lower OTR values of ~ 5.5
and ~ 9.8 ­cm3/m2∙day∙atm, respectively, at 20 °C/50% RH,
after isolation from their original starch granules [19]. How-
ever, the solution casting method for starch film formation is
quite time- and energy-consuming, particularly during the
solvent removal or drying processing [15]. These shortcom-
ings limit applications of starch films as barrier packaging
materials.
Thermoplastic starches (TPS) were normally prepared
using heat, and mechanical work to gelatinize and disrupt the
plasticized starch granules [20–29]. These TPS polymers are
considered as good packaging plastics for food, cosmetic and
pharmacy, because of their melt-processibilities and good
oxygen barrier properties [30–34]. For example, low OTRs
of ~ 121.3, ~ 79 and ~ 106.8 ­cm3/m2∙day∙atm at ~ 25 ℃/50%
RH were found for hot-pressed thermoplastic tapioca, corn
and potato starch films having a thickness of ~ 80, ~ 150
and ~ 35 μm, respectively [31–33]. While OTRs measured
at 25 ℃/50% RH for glycerol plasticized tapioca films hav-
ing a thickness of ~ 50 μm increased from 92.4 to 101.3 c­ m3/
m2∙day∙atm, as their glycerol loadings increased from 20
to 25wt% [34]. This unfavorably effect of glycerol on oxy-
gen barrier resistance of the plasticized tapioca films was
ascribed to the hygroscopic and plasticizer nature of glyc-
erol, which could increase the moisture content, free volume,
and enhance the OTRs of the glycerol plasticized tapioca
films [33, 34]. Nevertheless, most TPS or plasticized starch
films exhibited considerably poorer oxygen barrier resist-
ance than neat starch films, and rendered them unsatisfactory
for barrier packaging applications. This is likely due to the
hygroscopic and plasticizer nature of the overdosed plasti-
cizers in TPS or plasticized starch films. The most common
approach to improve the oxygen barrier properties of these
TPS or plasticized starch films is to blend with other high-
barrier and not expensive biodegradable thermoplastics,
such as polyvinyl alcohol (PVA) and poly ɛ-caprolactone
(PCL) [35–38]. The OTRs found for TPS (~ 100 μm) or
plasticized starch films (~ 120 μm) at ~ 23 ℃/ ~ 50% RH
were ~ 108.1 or ~ 66.5 ­cm3/m2∙day∙atm, respectively. After
blending 10wt% or 33.3wt% of PVA in TPS or plasticized
starch, the OTRs evaluated for TPS/PVA and plasticized
starch/PVA films reduced considerably to ~ 12.5 or ~ 26.5
­cm 3/m2∙day∙atm, respectively [35, 36]. However, these
13
Journal of Polymer Research (2021) 28: 475
OTRs were still not quite good enough for oxygen barrier
plastic applications.
Recent investigations have been demonstrating that gelati-
nization, modification or thorough disruption of molecular
organization of starch granules are facilitated with the assis-
tance of supercritical carbon dioxide ­(scCO2) in process-
ing [39–43]. This favorable processing is mainly ascribed
to the particularly low viscosity and high diffusivity of the
­scCO2 that can penetrate in local helices or double helices of
amylose and amylopectin molecules. Weakening hydrogen
bondings, especially disarrangement of hydrogen bondings
linking adjoining amylopectin double helices, turn favora-
bly with ­scCO2-assisted processing [44–48]. Presumably,
blending proper PVA loadings with s­ cCO2-assisted TPS
­(scCO2TPS) thermoplastics is anticipated to improve their
oxygen barrier resistance by favorably hydrogen-bonding
with loosely hydrogen-bonded -OH groups of these dissoci-
ated starch helix chains.
This current study investigated the oxygen barrier and
free volume characteristics of TPS, ­scCO2TPS, TPS/PVA
and ­s cCO 2TPS/PVA fully biodegradable blends. After
modification by PVA with varying degrees of polymeriza-
tion (DPs) and/or s­ cCO2-assisted processing, the OTRs and
free volume characteristics acquired for each series of TPS/
PVA and ­scCO2TPS/PVA blown films were considerably
improved and reduced to a minimum, as their PVA load-
ings approached an optimum value, respectively. The OTR
acquired for the optimum prepared ­scCO2TPS/PVA films
having a m­ c of 4wt% was only 4.6 ­cm3/m2∙day∙atm, which
is as good as polyvinylidene chloride oxygen barrier plas-
tics. In order to reveal the considerably improved oxygen
barrier and free volume characteristics of the TPS/PVA and
­scCO2TPS/PVA blown films, FTIR, DMA and WAXD char-
acterizations were performed to understand their molecular
interaction and crystallization behavior.
Experimental sections
Preparation of renewable barrier resins
Renewable tapioca starch (TS) granules were procured from
Eiambeng Tapioca Starch Industry Corporation. Three com-
mercial grades PVA resins denoted as P ­ VA03, ­PVA14 and
24
­PVA were provided by Taiwan Chang Chun Petrochemical
Corporation (CCPC). The P ­ VA03, ­PVA14 and P ­ VA24 resins
were estimated having 300, 800 and 1400 degrees of polym-
erization, respectively, by CCPC, and all PVA resins were
quoted with identical degree of hydrolysis of ~ 99 mol%. The
­ VA03, ­PVA14 and P
average molecular weights for P ­ VA24 res-
ins are summarized in Table 1. All acquired PVA resins were
refined by refluxing methanol for 4 h at 80 °C to take out
thermally unsteady impurities in the subsequent processing.
Journal of Polymer Research (2021) 28: 475
Table 1  Average molecular Grade of PVA Average
­ VA03, ­PVA14 and
weights of P molecular
24
­PVA resins weight
PVA03  ~ 13,200
PVA14  ~ 61,600
PVA24  ~ 105,600
All acquired PVAs were refined for 4 cycles before mixing
with TS.
Prior to s­ cCO2-assisted thermoplastic starch prepara-
tion, TS, purified water and glycerol were thoroughly mixed
at 5:3:2 weight ratio in a batch autoclave in air environ-
ment. Varying amounts of purified PVA resins were then
thoroughly mixed with the TS/water/glycerol compounds
before ­s cCO 2-assisted gelatinization and modification
processing. The air trapped in autoclave was then purged
away by flushing ­CO2 and then pressurized to a chosen
pressure of 9 MPa and a temperature of 100 °C. The TS/
water/glycerol/PVA compounds were processed in s­ cCO2
and magnetically stirring condition for 30 min to prepare
­scCO2-assisted TPS ­(scCO2TPS) and ­scCO2-assisted TPS/
PVA ­(scCO2TPSxPVAyz) thermoplastic starch materials. For
comparison purposes, TS/water/glycerol/PVA compounds
were gelatinized and modified at 5:3:2 weight ratio in an air
environment at 100 °C under magnetically stirring condi-
tion for 30 min to prepare conventional TPS and TPS/PVA
­(TPSxPVAyz) materials. The x and z shown in T ­ PSxPVAyz
y
and ­scCO2TPSxPVA z sample designations are the TPS and
PVA loading wt%, respectively; and y indicates the grade of
PVA applied in conventional or ­scCO2-assisted processes.
A Wuhan Tongchuang blown-film machine modelled
SJ20/28-BL26 was used for blowing the TPS, T ­ PSxPVAyz
y
­scCO2TPS and ­scCO2TPSxPVA z films. The barrel tempera-
tures were set at 140, 155, 170 and 185 ℃ from feeding inlet
to compression, extrusion zones and connector, respectively,
and the film-extrusion die was set at 180 °C before film-
blowing. For better preparation of the blown films, the TPS,
Fig. 1  The chart for prepa-
ration of ­TPSxPVAyz and
­scCO2TPSxPVAyz resins
Page 3 of 16 475
­scCO2TPS, ­TPSxPVAyz and ­scCO2TPSxPVAyz were dehy-
drated at 80 °C in an infrared drying oven for 8 h to achieve
a moisture content (­ mc) of ~ 10wt%. All films were blown
applying a blow-up ratio of 2 and a screw speed of 40 rpm in
all film-blowing processes. The blown films were controlled
to have a thickness of ~ 100 μm and an initial ­mc of ~ 4%.
The blown films were stored in a dehumidifier at 20 ℃/75%
relative humidity (RH) for 3 and 5 days, respectively, and
resulted in film samples having a ­mc of 9% and 14%. The
­mcs of TPS, s­ cCO2TPS, ­TPSxPVAyz and s­ cCO2TPSxPVAyz
films were measured using an infrared moisture meter at
temperatures ranging from 25 °C to 120 °C for 30 min. The
reported ­mc for each film was the average ­mc of five film
specimens. The films having varying m ­ cs were used to evalu-
ate their oxygen transmission rate. The chart for preparation
of ­TPSxPVAyz and ­scCO2TPSxPVAyz resins is illustrated in
Fig. 1.
Oxygen barrier properties
The OTRs of TPS, ­ s cCO 2 TPS, ­T PS x PVAy z and
y
­scCO2TPSxPVA z blown films having varying ­mcs were
evaluated at 25 °C/50% RH as suggested by ASTM D1434
by a Labthink Oxygen Permeability Analyzer modelled
VAC-V2. All OTR measurements were performed on circu-
lar films having a diameter of 10 cm. The OTR acquired for
each film sample was the average OTR of five blown films.
Free volume properties
Free volume properties of TPS, s­ cCO2TPS, ­TPSxPVAyz and
­scCO2TPSxPVAyz films were evaluated by an Oak Ridge
positron annihilation lifetime (PAL) instrument equipped
with a 22Na radiation source that was inserted on both sides
of several films to confirm comprehensive positron annihi-
lation in the film samples. Three lifespan components (i. e.
short- (τ1), intermediate- (τ2) and long-lifespan components
(τ3)) and annihilation intensity (AI) values representing
numbers of free volume holes per unit volume were resolved
13
475 Page 4 of 16
from PAL analyses. The τ1 and τ3 components were ascribed
to the para- and ortho-positronium (O-Ps) states, respec-
tively; while τ2 component was attributed to the free posi-
tron state. The radius, mean volume of the free volume holes
­(Rf, ­Vf) and free volume fraction (­ Fv) of TPS, s­ cCO2TPS,
­TPSxPVAyz and s­ cCO2TPSxPVAyz blown films were evalu-
ated from Eqs. (1) and (2) [49, 50], which assumed o-Ps
localizing in a spherical potential well having an electron
layer thickness of △R.
Rf
[ ( )]
1 1 2𝜋Rf
=2 1− + sin (1)
𝜏a Ro 2𝜋 Ro
where ΔR was given as 16.6 nm for all polymers [50], and
­Rf was the summation of ­R0 and ΔR.
The ­Fv was evaluated by Eq. (2) shown as follows [51,
52]:
Vf
Fv = = C × Vf × AI (2)
V
where C is a constant of 0.01 Å−3 for all polymers. The
evaluated experimental errors for τ3 and AI were ± 0.01 ns
and ± 0.05%, which yielded ± 0.91Å3 and ± 0.01% uncer-
tainties for evaluated ­Vf and F
­ v, respectively. Prior to PAL
analysis, all testing films were vacuum-dehydrated at 60 °C
for 20 min to yield an intentional ­mc of ~ 4%.
Fourier transform infrared spectroscopy
The molecular Interaction characteristics in PVA, TPS,
­scCO2TPS, ­TPSxPVAyz and s­ cCO2TPSxPVAyz films were
characterized using a Thermo Scientific Nicolet iS50 Fou-
rier transform infrared (FTIR) spectrometer. The TPS,
­scCO2TPS, ­TPSxPVAyz and s­ cCO2TPSxPVAyz films were
processed into small powders and mixed with KBr powders
at 1:100 weight ratio, and then pressed at 25 °C into films
having a thickness of ~ 200 μm, which was thin enough to
obey the Lambert–Beer law. All testing film samples were
vacuum-dehydrated at 60 °C for 20 min to yield an inten-
tional ­mc of ~ 4%. Thirty-two scans having a spectral resolu-
tion of 1 ­cm−1 were gathered and averaged during each FTIR
measurement.
Dynamic mechanical relaxations
The dynamic mechanical relaxations of all blown films hav-
ing a dimension of 60 × 10 × 0.1 mm were obtained using a
Q800 dynamic mechanical analyzer (DMA), which was pur-
chased from TA Instrument Corporation, New Castle, DE,
USA. All DMA experiments were performed at 1 Hz and a
heating rate of 3 °C/min under tension mode at temperatures
13
Journal of Polymer Research (2021) 28: 475
ranging from -50 to 150 ℃. Prior to DMA experiments, all
testing film samples were vacuum-dehydrated at 60 °C for
20 min to yield a ­mc of ~ 4%.
Wide angle x‑ray diffraction
Wide angle X-ray diffraction (WAXD) patterns of TS, PVA,
TPS, ­scCO2TPS, ­TPSxPVAyz and ­scCO2TPSxPVAyz films
(~ 100 μm) were acquired utilizing the Bruker D8 Advance
diffractometer furnished with Ni-filtered C ­ uKα radiation
operated at 40 kV and 100 mA. The film sample was kept
stationary and scanned the diffraction angle (2θ) from 5° to
30° at 25 °C, using a scanning rate of 5° per minute. Prior
to WAXD analysis, all testing film samples were vacuum-
dehydrated at 60 °C for 20 min to yield an intentional ­mc
of ~ 4%.
Results and discussion
Oxygen transmission rates
The OTRs evaluated for TPS, s­ cCO2TPS, ­TPSxPVAyz and
­scCO2TPSxPVAyz blown films at 4, 9 and 14wt% moisture
contents were displayed in Fig. 2. Relatively low OTR of
43.2 ­cm3/m2∙day∙atm was found for TPS film having a
moisture content of 4wt%. As expected, this OTR values
increased gradually to 62.1 and 78.9 ­cm3/m2∙day∙atm for
TPS films having higher ­mcs of 9 and 14wt%, respectively.
Compared to those OTRs of TPS films prepared without
­scCO2-assistance, quite lower OTRs of 40.8, 59.5 and 74.6
­cm3/m2∙day∙atm were found for s­ cCO2TPS blown films
having a m ­ c of 4, 9 and 14wt%, respectively. It is worth
noticing that OTRs obtained for T ­ PSxPVA03z, ­TPSxPVA14z
24
and ­TPSxPVA z series films with a fixed ­mc were reduced
to a minimum, as their PVA loadings approached an
optimum value of 25, 22.5 and 20wt%, respectively (see
Fig.  2). The OTRs acquired for the optimum prepared
­TPS75PVA0325, ­TPS77.5PVA1422.5 and ­TPS80PVA2420 hav-
­ c of 4wt% were 5.8, 9.2 and 10.7 c­ m3/m2∙day∙atm,
ing a m
respectively. Further lower OTRs values were found for the
corresponding ­scCO2TPSxPVA03z, ­scCO2TPSxPVA14z and
­scCO2TPSxPVA24z series films prepared with ­scCO2-assisted
processing. In fact, OTRs measured for the optimum pre-
pared ­scCO2TPS75PVA0325, ­scCO2TPS77.5PVA1422.5 and
­scCO2TPS80PVA2420 films having a ­mc of 4wt% reached as
low as 4.6, 5.1 and 8.4 ­cm3/m2∙day∙atm, respectively. These
OTRs are as good as polyvinylidene chloride oxygen bar-
rier plastics. All ­TPSxPVAyz and ­scCO2TPSxPVAyz series
films exhibited quite higher OTRs when they had higher
­mcs. For instance, OTRs measured for the optimum pre-
pared ­scCO2TPS75PVA0325, ­scCO2TPS77.5PVA1422.5 and
Journal of Polymer Research (2021) 28: 475
Fig. 2  Oxygen transmis-
sion rates of ­TPSxPVA03z
(,,), ­TPSxPVA14z (,,),
­TPSxPVA24z (△, △, △),
­scCO2TPSxPVA03z (▽, ▽,
▽), ­scCO2TPSxPVA14z (,,) and
­scCO2TPSxPVA24z (☆, ☆, ☆)
blown films having 4%, 9% and
14% moisture contents, respec-
tively. (Larger symbols indicate
higher moisture contents)
­scCO2TPS80PVA2420 films increased from 4.6, 5.1 and 8.4
­cm3/m2∙day∙atm to 35.6, 37.9 and 41.2 c­ m3/m2∙day∙atm,
respectively, as their moisture contents increased from 4wt%
to 14wt%.
FTIR characterizations
Figures 3, 4 and 5 displayed typical FTIR spectra char-
acterized for PVA, TPS, ­T PS xPVAyz, ­s cCO 2TPS and
­scCO2TPSxPVAyz film specimens. Similar to the findings
in previous studies [47, 53], distinctive O–H stretching,
C-H stretching, -CH2- bending and C-O stretching absorp-
tion bands of PVA with varying DPs centered at 3444,
2939, 1468 and 1093 ­cm−1, respectively, were found on
FTIR spectra of PVA with varying DPs (see Figs. 3s, 4q
and 5s). Distinguishing absorption bands peaked at 3434,
2943, 1639, 1040 and 1454 ­cm−1 originated from O–H,
C-H, H–O-H, C-O stretching and -CH2- bending vibration
motions, respectively, were observed in FTIR spectra of TPS
specimens [54]. Similar distinctive absorption bands could
be found for s­ cCO2TPS specimen, however, the magnitude
and peak ­cm−1 associated with the O–H stretching bands
were substantially larger than that of TPS prepared with-
out ­scCO2-assistance. In addition, the peak c­ m−1 associated
with C-O stretching band of ­scCO2TPS specimen reached
1043 ­cm−1, which was slightly larger than that (~ 1040 ­cm−1)
of TPS specimen.
After PVA modification, the peak c­ m−1 of O–H stretching
bands for ­TPSxPVA03z, ­TPSxPVA14z and ­TPSxPVA24z speci-
mens were reduced considerably from 3434 ­cm−1 to 3416,
Page 5 of 16 475
3419 and 3421 ­cm−1, as their PVA loadings increased from
0wt% to 25, 22.5 and 20wt%, respectively (see Figs. 3a-
i, 4a-h and 5a-i). Similar PVA loading dependence on
the movement of peak c­ m−1 for O–H stretching bands was
found for each s­ cCO2TPSxPVAyz series, and their peak
­cm−1 for O–H stretching bands reduced considerably from
3444 ­cm−1 to a minimum of 3413, 3417 and 3419 ­cm−1, as
the PVA loadings of s­ cCO2TPSxPVA03y, ­scCO2TPSxPVA14y
and ­scCO2TPSxPVA24y series increased from 0wt% to the
optimum loading of 25, 22.5 and 20wt%, respectively. It
is worth noticing that the peak c­ m−1 of the optimum pre-
pared ­scCO2TPS75PVA0325, ­scCO2TPS77.5PVA1422.5 and
­scCO2TPS80PVA2420 specimens reduced gradually as PVA’s
DPs diminished from 2400 to 1400 and 300. Similarly, the
magnitudes for O–H stretching bands of s­ cCO2TPSxPVAyz
series specimens were substantially larger than those of the
equivalent ­TPSxPVAyz series specimens having identical
PVA loadings and DP values.
The movement of O–H and C-O stretching bands toward
larger peak ­cm−1 for ­scCO2TPS has been recognized as
the weakening or lengthening of intra- and intermolecular
hydrogen-bondings in TPS [43, 55–57]. Whereas the move-
ment of O–H stretching bands toward smaller peak ­cm−1
for ­TPSxPVAyz and ­scCO2TPSxPVAyz is ascribed to the
enhancement of O–H hydrogen-bondings between starch and
PVA chains [46, 47]. Particularly, enhanced O–H hydrogen
bonds may be discovered between starch’s lengthened O–H
groups and PVA’s O–H groups in s­ cCO2TPSxPVAyz series.
The enormously large diffusivities and/or small viscosi-
ties of supercritical ­CO2 are expected to result in favorable
13
475 Page 6 of 16 Journal of Polymer Research (2021) 28: 475

Fig. 3  FTIR spectra of (a)

TPS, (b) ­TPS95PVA035,
(c) ­TPS90PVA0310, (d)
­TPS85PVA0315, (e)
­TPS80PVA0320, (b)
­TPS77.5PVA0322.5, (g)
­TPS75PVA0325, (h)
­TPS72.5PVA0327.5, (i)
­TPS70PVA0330, (j) ­scCO2TPS,
(k) ­scCO2TPS95PVA035, (l)
­scCO2TPS90PVA0310, (m)
­scCO2TPS85PVA0315, (n)
­scCO2TPS80PVA0320, (o)
­scCO2TPS77.5PVA0322.5, (p)
­scCO2TPS75PVA0325, (q)
­scCO2TPS72.5PVA0327.5, (r)
­scCO2TPS70PVA0330 and (s)
­PVA03 specimens

penetration of plasticization (e. g. water, PVA and glycol)
or reactant, and cause effective plasticization in amorphous
regions of starch granules. Disruption of hydrogen-bondings
in adjacent single or double helices of starch chains, is
considerably easier with ­scCO2-assistance in the gelati-
nization processing of s­ cCO2TPS and s­ cCO2TPSxPVAyz.
Therefore, more weakened or free starch hydrogen-bonded
-OH groups were found in FTIR spectra of ­scCO2TPS
and ­scCO2TPSxPVAyz compared to TPS and ­TPSxPVAyz,
respectively. These loosely -OH hydrogen-bondings could
be replaced and developed stronger hydrogen-bondings
with PVA’s -OH groups in the preparation processing of
­scCO2TPSxPVAyz. Besides, PVA having smaller DPs could
have more favorable penetration, and cause more efficient
plasticization in starch amorphous regions by formation
of stronger hydrogen bonds with the weakened starch -OH
groups. Consequently, the peak c­ m−1 of the optimum pre-
pared ­scCO2TPS75PVA0325, ­scCO2TPS77.5PVA1422.5 and
­scCO2TPS80PVA2420 specimens reduced gradually, as PVA’s
DPs diminished from 2400 to 1400 and 300.
Dynamic mechanical analysis
Dynamic mechanical relaxations of PVA, TPS, ­scCO2TPS,
­TPSxPVAyz and ­scCO2TPSxPVAyz films are illustrated in
Figs. 6, 7, 8, 9, 10 and 11. The neat TPS and PVA films dis-
played a distinct dynamic glass-transition temperature ­(Tg)
at ~ 58 and ~ 90 ℃, respectively. Merely a ­Tg transition was
found for each T­ PSxPVAyz series films, when their PVA load-
ings were ≦ the equivalent optimum value, respectively. As

13
Journal of Polymer Research (2021) 28: 475 Page 7 of 16 475

hydrogen bonds of PVA’s -OH groups with the loosely or

free starch -OH groups found for ­scCO2TPSxPVAyz, since
favorable disruption of hydrogen-bondings in adjacent
single or double helices of starch chains is anticipated in
­scCO2-assisted gelatinization processes of s­ cCO2TPS and
­scCO2TPSxPVAyz. In addition, PVA having smaller DPs
could have more favorable penetration, and lead to more
efficient plasticization in starch amorphous regions by
formation of stronger hydrogen bonds with the weakened
starch -OH groups. Consequently, the single ­Tgs found for
­scCO2TPSxPVAyz films were higher than those of corre-
sponding ­TPSxPVAyz films with identical PVA loadings,
and were reduced further with the decrease in PVA’s DPs.

Wide angle X‑ray diffraction

Figures 12, 13 and 14 display typical WAXD patterns for

tapioca starch, PVA, TPS, ­T PS xPVAyz, ­s cCO 2TPS and
­scCO2TPSxPVAyz films. As shown in Figs. 12t, 13r and
14t, diffraction peaks (2θ) located at 11.5°, 16.1°, 19.2°,
20.0° and 22.7° were found for neat PVA having varying
DPs. These diffraction peaks are reported to derive from
Fig. 4  FTIR spectra of (a) TPS, (b) ­TPS95PVA145, (c) ­TPS90
PVA1410, (d) ­TPS85PVA1415, (e) ­TPS80PVA1420, (f) ­TPS77.5PVA1422.5,
(g) ­TPS75PVA1425, (h) ­TPS70PVA1430, (i) ­scCO2TPS, (j) ­scCO2
TPS95PVA145, (k) ­scCO2TPS90PVA1410, (l) ­scCO2TPS85PVA1415,
(m) ­scCO2TPS80PVA1420, (n) ­scCO2TPS77.5PVA1422.5, (o) ­scCO2TPS75
PVA1425, (p) ­scCO2TPS70PVA1430 and (q) ­PVA14 specimens

­ PSxPVA03z series films reduced from

shown in Fig. 6, ­Tgs for T
58 to 31 ℃, as PVA loadings increased from 0 to the optimum
value of 25wt%. It is interesting to note that these single ­Tgs
were much lower than that of the neat TPS, and became fur-
ther lower as PVA loadings increased. Similar findings have
been reported by Hodge and coauthors [58], this decrease in
­Tgs for ­TPSxPVAyz series films was ascribed to the efficient
plasticization effect of PVA for starch.
Two distinctive dynamic T ­ gs were observed for each
­TPSxPVAyz series films, when PVA loadings were larger
than their optimum values. Both distinct ­Tgs moved toward
those ­Tgs detected for TPS and PVA polymers, undoubt-
edly indicating two existing mixed and separated phases.
Similar PVA loading dependence of dynamic ­Tgs was found
for ­scCO2TPSxPVAyz series films, while higher dynamic T ­ gs
were found for the ­scCO2TPSxPVAyz series films compared
to those of corresponding T ­ PSxPVAyz series films prepared
Fig. 5  FTIR spectra of (a) TPS, (b) ­TPS95PVA245, (c) ­TPS90PVA2410,
without the assistance of ­scCO2 (see Figs. 9, 10 and 11). (d) ­TPS85PVA2415, (e) ­TPS82.5PVA2417.5, (f) ­TPS80PVA2420, (g) ­TPS77.5
These dynamic transition results demonstrate that TPS and PVA2422.5, (h) ­TPS75PVA2425, (i) ­TPS70PVA2430, (j) ­scCO2TPS, (k)
PVA having various DPs are compatible for T ­ PSxPVAyz and ­scCO2TPS95PVA245, (l) ­scCO2TPS90PVA2410, (m) ­scCO2TPS85PVA2415,
y (n) ­scCO2TPS82.5PVA2417.5, (o) ­scCO2TPS80PVA2420, (p) ­scCO2
­scCO2TPSxPVA z films, when their PVA loadings are ≦ the
TPS77.5PVA2422.5, (q) ­scCO2TPS75PVA2425, (r) ­scCO2TPS70PVA2430 and
corresponding optimum values. The higher dynamic T ­ gs for (s) ­PVA24 specimens
­scCO2TPSxPVAyz series films is attributed to the stronger

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475 Page 8 of 16 Journal of Polymer Research (2021) 28: 475

Fig. 6  Temperature
dependence of tan δ of (a)
TPS, (b) ­TPS95PVA035,
(c) ­TPS90PVA0310,
(d) ­TPS85PVA0315,
(e) ­TPS80PVA0320, (f)
­TPS77.5PVA0322.5, (g)
­TPS75PVA0325, (h)
­TPS72.5PVA0327.5, (i)
­TPS70PVA0330 and (j) ­PVA03
specimens

the diffraction of α-form PVA unit cell structure [59]. As
shown in Figs. 12a, 13a and 14a, located at 2θ = 10.6°, 11.5°,
15.1°, 23.0° and a doublet at 17.1°, 18.0° were found on
WAXD pattern of TS granules. These distinguishable dif-
fraction peaks were primarily ascribed to the diffraction of
A-type starch crystals [60–62], and a smaller diffraction con-
tribution derived from B-type starch crystals having distinct
diffraction peaks at ~ 10.6° and ~ 11.5° [60, 61]. These dif-
fraction peaks of starch crystals vanished completely in
WAXD patterns of thermoplastic TPS and s­ cCO2TPS films
(see Figs. 12b, 13b and 14b for TPS and 12(k), 13(j) and
14(k) for ­scCO2TPS). Distinct diffraction peaks located at
2θ = 12.7°, 19.5° and 21.0° appeared in WAXD patterns
of TPS and ­TPSxPVAyz, which might result from induced

Fig. 7  Temperature
dependence of tan δ of (a)
TPS, (b) ­TPS95PVA145,
(c) ­TPS90PVA1410,
(d) ­TPS85PVA1415,
(e) ­TPS80PVA1420, (f)
­TPS77.5PVA1422.5, (g)
­TPS75PVA1425, (h)
­TPS70PVA1430 and (i) ­PVA14
specimens

13
Journal of Polymer Research (2021) 28: 475 Page 9 of 16 475

Fig. 8  Temperature
dependence of tan δ of (a)
TPS, (b) ­TPS95PVA245,
(c) ­TPS90PVA2410,
(d) ­TPS85PVA2415,
(e) ­TPS82.5PVA2417.5,
(f) ­TPS80PVA2420,
(g) ­TPS77.5PVA2422.5,
(h) ­TPS75PVA2425, (i)
­TPS70PVA2430 and (j) ­PVA24
specimens

crystallization of V
­ h-type starch crystals by PVA [61–63].
It is worth emphasizing that the magnitudes of these dif-
fraction peaks increased significantly with increasing PVA
loadings (see Figs. 12c-j, 13c-i and 14c-j). Accordant with
the dynamic transitions found in the previous sections, dif-
fraction peaks at 11.0° and 22.9°of α-form PVA crystallinity
gradually appeared in WAXD patterns of ­TPSxPVA03z,
­TPSxPVA14z and T ­ PSxPVA24z films, when their PVA load-
ings were greater than the corresponding optimum value of
25, 22.5 and 20wt%, respectively (see Figs. 12i-j, 13h, i and
14h-j). In addition, the magnitudes of starch ­Vh-type diffrac-
tion peaks for s­ cCO2TPS and s­ cCO2TPSxPVAyz films were

Fig. 9  Temperature depend-
ence of tan δ of (a) ­scCO2TPS,
(b) ­scCO2TPS95PVA035, (c)
­scCO2TPS90PVA0310, (d)
­scCO2TPS85PVA0315, (e)
­scCO2TPS80PVA0320, (f)
­scCO2TPS77.5PVA0322.5, (g)
­scCO2TPS75PVA0325, (h)
­scCO2TPS72.5PVA0327.5, (i)
­scCO2TPS70PVA0330 and (j)
­PVA03 specimens

13
475 Page 10 of 16 Journal of Polymer Research (2021) 28: 475

Fig. 10  Temperature depend-
ence of tan δ of (a) ­scCO2TPS,
(b) ­scCO2TPS95PVA145, (c)
­scCO2TPS90PVA1410, (d)
­scCO2TPS85PVA1415, (e)
­scCO2TPS80PVA1420, (f)
­scCO2TPS77.5PVA1422.5, (g)
­scCO2TPS75PVA1425, (h)
­scCO2TPS70PVA1430 and (i)
­PVA14 specimens

significantly smaller than those observed in WAXD patterns
of TPS and ­TPSxPVAyz films having identical composi-
tions. Similar to those found in WAXD patterns ­TPSxPVAyz
films, the magnitudes of starch ­Vh-type diffraction peaks for
­scCO2TPSxPVAyz films grew significantly with increasing
PVA loadings (see Figs. 12l-s, 13k-q and 14l-s). In addition,
diffraction peaks at 11.0° and 22.9° for α-form PVA crystals
appeared gradually in WAXD patterns of ­scCO2TPSxPVA03z,
­scCO2TPSxPVA14z and s­ cCO2TPSxPVA24z films, when their
PVA loadings were greater than the corresponding optimum
value of 25, 22.5 and 20wt%, respectively (see Figs. 12r, s,
13p, q and 14q-s).

Fig. 11  Temperature depend-
ence of tan δ of (a) ­scCO2TPS,
(b) ­scCO2TPS95PVA245, (c)
­scCO2TPS90PVA2410, (d)
­scCO2TPS85PVA2415, (e)
­scCO2TPS82.5PVA2417.5, (f)
­scCO2TPS80PVA2420, (g)
­scCO2TPS77.5PVA2422.5, (h)
­scCO2TPS75PVA2425, (i)
­scCO2TPS70PVA2430 and (j)
­PVA24 specimens

13
Journal of Polymer Research (2021) 28: 475 Page 11 of 16 475

Fig. 12  WAXD pattern
of (a) tapioca starch, (b)
TPS, (c) ­TPS95PVA035,
(d) ­TPS90PVA0310,
(e) ­TPS85PVA0315, (f)
­TPS80PVA0320, (g)
­TPS77.5PVA0322.5, (h)
­TPS75PVA0325, (i)
­TPS72.5PVA0327.5, (j)
­TPS70PVA0330, (k) ­scCO2TPS,
(l) ­scCO2TPS95PVA035, (m)
­scCO2TPS90PVA0310, (n)
­scCO2TPS85PVA0315, (o)
­scCO2TPS80PVA0320, (p)
­scCO2TPS77.5PVA0322.5, (q)
­scCO2TPS75PVA0325, (r)
­scCO2TPS72.5PVA0327.5, (s)
­scCO2TPS70PVA0330 and (t)
­PVA03

The dynamic mechanical relaxations and WAXD
characterization of T­ PS x PVAy z and s­ cCO 2 TPS x PVAy z
blends revealed that PVA and TPS were compatible, as
PVA loadings were ≤ the optimum value. The most con-
vincing argument for compatibility in T ­ PS xPVAyz and
y
­scCO2TPSxPVA z blends with PVA loadings ≤ the corre-
sponding optimum value is the singular and intermediate
dynamic glass transition temperature. In addition, PVA
did not crystallize in cooling processes of ­T PS xPVAyz
and ­s cCO 2TPS xPVAyz blown films and only TPS crys-
tals crystallized at PVA loadings < the corresponding
optimum value. Whereas PVA and TPS were anticipated
to crystallize independently, when PVA loadings were
sufficiently high in each incompatible ­T PS xPVAyz and
­scCO2TPSxPVAyz film series. Finally, it is worth noticing
that the optimum PVA loading of each T ­ PS xPVAyz and
y
­scCO2TPS xPVA z film series increased from 20 to 22.5
and 25wt%, when PVA’s DPs diminished from 2400 to
1400 and 300, respectively. It is likely that PVA having
smaller DPs is anticipated to have lower intrinsic viscosi-
ties and can interact more thoroughly with TPS in the
film-blowing process. Consequently, significant increase
in optimum PVA loading was found for ­TPSxPVAyz and
­scCO2TPSxPVAyz blends, as their PVA’s DPs decreased.
Free volume properties
As shown in Figs. 15, 16, 17 and 18 the free volume char-
acteristics (i. e., AI, ­Rf, ­Vf and F
­ v) of TPS and s­ cCO2TPS
blown films were noticeably larger than those of the neat
PVA blown films. Compared to TPS blown films, AI, ­Rf, ­Vf
and ­Fv evaluated for ­scCO2TPS blown films were noticeably
smaller. It is worth noticing that all free volume character-
istics of ­TPSxPVA03z and ­scCO2TPSxPVA03z blown films

13
475 Page 12 of 16 Journal of Polymer Research (2021) 28: 475

Fig. 13  WAXD pattern
of (a) tapioca starch, (b)
TPS, (c) ­TPS95PVA145,
(d) ­TPS90PVA1410,
(e) ­TPS85PVA1415, (f)
­TPS80PVA1420, (g)
­TPS77.5PVA1422.5, (h)
­TPS75PVA1425, (i)
­TPS70PVA1430, (j) ­scCO2TPS,
(k) ­scCO2TPS95PVA145, (l)
­scCO2TPS90PVA1410, (m)
­scCO2TPS85PVA1415, (n)
­scCO2TPS80PVA1420, (o)
­scCO2TPS77.5PVA1422.5, (p)
­scCO2TPS75PVA1425, (q)
­scCO2TPS70PVA1430 and (r)
­PVA14

decreased to a minimum, as ­PVA03 loadings approached an
optimum value of 25wt%. Similar PVA loading dependence
of the free volume characteristics was found for T­ PSxPVAyz
y
and ­scCO2TPSxPVA z blown films, while the optimum PVA
loadings yielding the smallest free volume characteristics
for ­TPSxPVA14z (or ­scCO2TPSxPVA14z) and ­TPSxPVA24z
(or ­scCO2TPSxPVA24z) blown film series were reduced to
22.5wt% and 20wt%, respectively. Furthermore, the small-
­ PSxPVAyz
est free volume characteristics evaluated for the T
y
and ­s cCO 2TPS xPVA z blown films reduced noticeably
with diminishing DPs for PVA. As shown in Figs.  17
and 18, the ­Rf (or ­Fv) evaluated for T ­ PS75PVA0325 and
03
­scCO2TPS75PVA 25 blown films were 3.11 Å (or ~ 10.3%)
and ~ 2.64  Å (or ~ 7.9%), respectively, which were quite
smaller than those evaluated for TPS and s­ cCO2TPS blown
films without modification by PVA.
All free volume characteristics, especially R ­ f or F
­v
are generally anticipated to play a key role for OTRs of
­T PS xPVAyz and s­ cCO 2TPS xPVAyz blends. The oxygen
molecules having a radius of ~ 2 Å could permeate through
these free volume holes more difficult as these free vol-
ume characteristics were reduced. The considerably
enhanced oxygen barrier resistance found for T ­ PSxPVAyz
y
and ­scCO2TPSxPVA z blown films having proper compo-
sitions was most likely due to their noticeably diminished
free volume characteristics. We propose that the dimin-
ished free volume characteristics acquired for ­TPSxPVAyz
and ­scCO2TPSxPVAyz blown films may be at least partly
due to the strengthened intermolecular interactions between
hydroxyl groups of TPS and PVA, as they were processed
with the assistance of ­scCO2, optimum PVA loadings or
diminished DPs.

13
Journal of Polymer Research (2021) 28: 475 Page 13 of 16 475

Fig. 14  WAXD pattern
of (a) tapioca starch, (b)
TPS, (c) ­TPS95PVA245,
(d) ­TPS90PVA2410,
(e) ­TPS85PVA2415, (f)
­TPS80PVA2417.5, (g)
­TPS77.5PVA2420, (h)
­TPS75PVA2422.5, (i)
­TPS72.5PVA2425, (j)
­TPS70PVA2430, (k) ­scCO2TPS,
(l) ­scCO2TPS95PVA245, (m)
­scCO2TPS90PVA2410, (n)
­scCO2TPS85PVA2415, (o)
­scCO2TPS80PVA2417.5, (p)
­scCO2TPS77.5PVA2420, (q)
­scCO2TPS75PVA2422.5, (r)
­scCO2TPS72.5PVA2425, (r)
­scCO2TPS70PVA2430 and (t)
­PVA24

Fig. 15  The annihilation intensity (AI) ­[TPSxPVA03z (■), ­TPSxPVA14z (Vf) ­[TPSxPVA03z (●), ­
Fig. 16  The volume ­ TPSxPVA14z (●), ­ TPSx
(■), ­TPSxPVA24z (■), ­scCO2TPSxPVA03z (□), ­scCO2TPSxPVA14z (□) PVA24z (●), s­cCO2TPSxPVA03z (○), ­scCO2TPSxPVA14z (○) and s­cCO2
and ­scCO2TPSxPVA24z (□)] of the free-volume-cavities of T ­ PSxPVAyz TPSxPVA24z (○)] of the free-volume-cavities of ­ TPSxPVAyz and
and ­scCO2TPSxPVAyz film specimens ­scCO2TPSxPVAyz film specimens

13
475 Page 14 of 16
(Rf) ­[TPSxPVA03z (▲), ­TPSxPVA14z
Fig. 17  The average radius ­
(▲), ­TPSxPVA z (▲), ­scCO2TPSxPVA03z (△), ­scCO2TPSxPVA14z
24
(△) and s­cCO2TPSxPVA24z (△)] of the free-volume-cavities of
­TPSxPVAyz and ­scCO2TPSxPVAyz film specimens
Fig. 18  The fractional free-volume (­ Fv) ­[TPSxPVA03z (▼), ­TPSxPVA14z
(▼), ­TPSxPVA24z (▼), s­cCO2TPSxPVA03z (▽), ­scCO2TPSxPVA14z
(▽) and s­cCO2TPSxPVA24z (▽)] of the free-volume-cavities of
­TPSxPVAyz and ­scCO2TPSxPVAyz film specimens
Conclusions
The oxygen barrier and free volume properties acquired
for ­TPS xPVAyz and ­s cCO 2TPS xPVAyz blown films were
considerably improved after modification by PVA with
varying DPs and/or ­s cCO 2 -assisted processing. The
OTRs and all free volume characteristics of T­ PSxPVA03z,
14
­T PS x PVA z and T ­ PS x PVA z (or s­ cCO 2 TPS x PVA 03 z ,
24
­scCO2TPSxPVA z and s­ cCO2TPSxPVA24z) blown films
14
13
Journal of Polymer Research (2021) 28: 475
were considerably improved and reduced to a minimum,
as their PVA loadings approached an optimal value of 25,
22.5 and 20wt%, respectively. Compared to T ­ PSxPVAyz,
OTRs and free volume characteristics of correspond-
ing ­s cCO 2 TPS x PVAy z blown films were considerably
smaller. The minimum OTR and free volume character-
istic acquired for the optimum prepared T ­ PSxPVAyz and
y
­s cCO 2TPS xPVA z films were found to decrease notice-
ably with diminished DPs of PVA. An important out-
come is that the OTR acquired for the optimum prepared
­s cCO 2TPS xPVAyz films having a ­m c of 4wt% was only
4.6 ­cm3/m2∙day∙atm, which is comparable to that of the
polyvinylidene chloride oxygen barrier plastics.
The dynamic mechanical relaxations and WAXD
characterization of ­T PS x PVAy z and s­ cCO 2 TPS x PVAy z
blends revealed that PVA and TPS were compatible, as
PVA loadings were ≤ the optimum value. The most con-
vincing argument for compatibility in ­T PS xPVAyz and
­scCO2TPSxPVAyz blends with PVA loadings ≤ the corre-
sponding optimum value is the singular and intermediate
dynamic glass transition temperature. In addition, PVA
did not crystallize in cooling processes of T ­ PS xPVAyz
y
and ­s cCO 2TPS xPVA z blown films and only TPS crys-
tals crystallized at PVA loadings ≤ the corresponding
optimum value. Whereas PVA and TPS were anticipated
to crystallize independently, when PVA loadings were
sufficiently high in each incompatible T ­ PS xPVAyz and
y
­scCO2TPSxPVA z film series. Finally, it is worth noticing
that the optimum PVA loadings of each ­TPSxPVAyz and
­s cCO 2TPS xPVAyz film series increased from 20 to 22.5
and 25wt%, when PVA’s DPs diminished from 2400 to
1400 and 300, respectively. It is likely that PVA having
smaller DPs is anticipated to have lower intrinsic viscosi-
ties and can interact more thoroughly with TPS in the
film-blowing process. Consequently, significant increase
in optimum PVA loading was found for ­TPSxPVAyz and
­scCO2TPSxPVAyz blends, as their PVA’s DPs decreased.
The diminished OTRs and free volume characteristics for
­TPSxPVAyz and s­ cCO2TPSxPVAyz blown films may be at
least partly due to the strengthened intermolecular interac-
tions between hydroxyl groups of TPS and PVA, as they
were processed with the assistance of ­s cCO 2, optimum
PVA loadings or diminished DPs.
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